The Pokémon Gold and Silver remakes, HeartGold and SoulSilver, offer two instances; one intentional and one that's rather disturbing:
The intentional occasion takes place when the player reaches the day care couple for the first time and are greeted by either Gold/Ethan or Lyra (depending on player gender) after a brief conversation, their grandfather will comment about them having a crush on the player character. Naturally they'll force their grandparents to change the topic then run out in embarrassment.
The unintentional instance occurs when trying to infiltrate Team Rocket's radio tower in disguise only for Silver (the rival) to run in and forcefully strip the player character. Granted he's only trying to remove the Rocket uniform since he despises the organization and can't see his rival among their ranks, still this scene alone has managed to generate hundreds of Silver/Lyra and Silver/Gold drawings.
Playing as May, the female character, in Pokémon Emerald, Brendan will state how he saw a Pokémon, Rayquaza, and wish you were there to see it with him.
In Pokémon Diamond and Pearl, one of the villain team's Commanders says, "So what is it? Are you some lovey-dovey couple to the rescue?", in a scene where you are with one of your rivals, the one that is the opposite gender's playable character.
There is also a scene in HGSS where resident Memetic Sex Goddess Cynthia mentions that your eyes remind her of someone from Sinnoh.
There is a ferris wheel on which you ride with a different NPC each season. The NPC choices vary with gender (including one that is your own gender), and the conversations on the ride are loaded with Double Entendres.
Black 2/White 2 features its own set. The Dropped Itemsidequest will eventually result in a blushing NPC and a slew of conversations that make her/his attraction blatantly obvious. Yancy even sings a song called "Xtransceiver Love" as Nancy on the Celebrity channel.
For RangerShipping (Solana x Lunick) fans, you've got not only the various little hints throughout the game, you've also got the Groudon mission. Same with the Kyogre mission for Solana/Lunick x Aria fans.
Shadows of Almia has a bit of VatonageShipping/RangerSchoolShipping (Kate x Keith and Kellyn x Keith) too.
Guardian Signs dabbles in a bit of ObliviaShipping (Ben x Summer) too: Nema teases Ben and Summer that they are going on a date when out on patrol. Whichever one is not the player character begins talking quickly and getting flustered.
Back in the early days, there was Ash/Misty teasing going on since about the eighth episode (especially with 4Kids going out of its way to create extra evidence).
One of the most prominent examples is when the end of summer festival episode (the Ghost of Maiden's Peak to be precise). Ash sees Misty in a yakata, with her hair down, and his reaction could not have been more Shoujo...
Misty's jealous reaction to Melody flirting with Ash in the second movie.
And how about the time Team Rocket teased Ash and Misty on their airship?
A double whammy for Ash/Misty in episode 198 of the original series: When Brock meets a girl who falls in love with him, she talks about how she wants to marry Brock. Ash makes an offhanded comment about how weird it would be if Brock got married. Misty then says "You and I will be married someday, too." Ash first nods his head, then reacts accordingly when he realizes just how Misty said it (This). Of course, her dialogue was very different in the Japanese version, but it still counts as 4Kids-fuelled tease at least.
Another 4Kids dub moment — in Pokémon: Jirachi Wishmaker, Ash talks with Max about the inevitability of having to part ways with some friend, using the example of a particular girl whom he misses constantly and thinks about daily. (In the original Japanese, Satoshi is speaking in general about all the friends he's made, not just one particular individual).
In a Pokemon Chronicles episode, Misty is approached by a young man looking to ask her out on a date. Her response is an attempt to awkwardly turn him down, in which the question of another man is raised (and Misty's Psyduck has no little bit of fun with this). Granted, this could be interpreted for any male character, and some did think that the comment was with regard to Tracey, but those were in the minority and there were no other alternatives favored by the fandom.
Back when it was still under the 4Kids banner, many of the extra materials threw their weight behind this. Misty has at least two Image Songs about Ash, and the two shared a duet on the Christmas CD (about mistletoe, no less).
Pokémon Colosseum has Eagun, an Old Master who started off with a Pikachu. His granddaughter bears a rather striking resemblance to Misty. A possible inter-continuity nod?
Particularly in the episode "Two Degrees of Separation" where in one instance Brock introduces Ash to a female driver named Claudina who he'd been hoping to score with. Interesting to note that in the entire time he's doing so he's being all touchy feely with Ash, hugging him close and poking and prodding at his face in a playful manner. Later, he finds out that Claudina already has a boyfriend and she drives away. Which leads to this scene from the English dubbed version.
In the episode Love at First Flight May tricked Ash into dressing up as a woman they had just met, named Juliet, in order to help a man named Romeo confess the feelings that he had for Juliet. Brock tried to help out too and ended up getting carried away,even chasing poor Ash around and trying to hug him while declaring "My sweet Juliet! Heal me with your love!" *releases hearts*
Also, thanks to the No Hugging, No Kissing policy the show often has in play, the best Ash can usually get with the girls is hand-holding (or in Dawn's case, a high-five). So when he and Brock bid each other farewell in the final DP episode (first shaking hands, then gripping them close together, before slowly pulling apart to go their separate ways), you can only imagine how the Yaoi Fangirls took it. It can, of course, be seen as a mark of their brotherly bond, which practically receives its own subplot during DP (thanks to all their nice moments together). Whether you're a shipper or not, you can definitely appreciate how the writers recognised the close bond Ash and Brock shared by this point.
There have been a few instances of Ship Tease between Ash and Dawn.
During Ash's earlier Gym battles, Dawn cheers (no, not just praises him, actually dresses in a cheerleading outfit, along with some of her other Pokemon) for Ash.
Lyra brings up the idea of an actual relationship with Ash, and asks Dawn if the two of them are already in a relationship. Dawn gets oddly defensive at that point.
The Diamond and Pearl opening theme High Touch! pretty much sounds like one big Ship Tease between Ash and Dawn.
Best Wishes wasted no time in throwing out some Ash/Iris Ship Tease right in the third episode. Sadly, there weren't as many hints here than with Ash's other female companions.
Justified in that dark skinned girls are not the type of girls to blush and/or get googly eyed when they legitimately like someone. That being said, Iris did get googly eyed briefly when she thought Ash was gonna get killed.
Cilan seemed really excited to join Ash's team, and seemed rather exuberant after Ash won the gym battle against him.
Combine the above two with Cilan/Iris in the "other hetero" folder below, and you get a rare One True Threesome for Ash that does not involve Pikachu. In the two-parter "Rocking the Virbank Gym" (where Ash battles Roxie for his 8th badge), not only does Iris leave the room to get a big-ass drum to bang and cheer Ash, but then when it really looks like he's going to lose, she has herself, Axew and Cilan made-up with paint to stand out as his personal cheering squad, banging drums and rekindling his spirit, enabling him to pull a win! It really beats any one of Dawn's cheerleading sessions! And given how Cilan helped Iris out (albeit a bit awkwardly)...
Hints that Ash and Serena may be Childhood Friends created ship tease before the XY anime even aired. The friendship ultimately turned out to be just spending one summer-camp together, but that just makes the early hints on Serena's side all the more powerful. Ash really made an impression on her.note What happened was something like this: when they were just kids and at summer-camp together, Serena got lost in the woods and hurt her knee. Ash found her and used a handkerchief to treat her knee. When finished, Serena was afraid to walk, so he took her hands and got her on her feet again, but used a little bit too much force. She crashed into him, ending up in what was basically a hug, something that Serena was very much aware of. He then led her back to the camp, still holding hands. In the years afterwards, Serena never forgot about the incident and when she saw Ash on television at the beginning of the season (XY002), she uses the start of her own pokémon journey as a means of meeting him again and, when she indeed finds him, returning his handkerchief to him.
Serena showed too many hints for Ash, blushing, acting shy, admiring him from afar and others. Here's a list, but it's notable that she's done one thing on-camera that we've hardly seen any of her potential rivals do: cook for him.note Ok, technically, Misty did make him dinner once on-camera and medicine one other time. That's 2 out of over 270 episodes, with one of those having her fall prey to Oven Logic. Serena matched that total in episode ten of her arc and her cooking's been perfect thus far.
It's confirmed she has "special feelings" and is "very interested" in him. In other words, Serena has a canon crush on Ash.
Given that Serena's only been on-screen for about two dozen episodes as of April 2014, this is the couple with the highest Ship Tease per episode rating, Serena gives a hint almost every episode! People are betting a lot that this pair will become canon.note Though they tend to forget that Serena's biggest "rival" is no girl, guy, or mon, but Ash's Chaste Hero status.
In the official character connection table, the line connecting Serena to Ash is marked◊ スキ...?note Japanese for "Likes...?" Shippers will argue that 'suki' can also be translated as "loves". It's also notable that the line in question is Pink. The fact that they made a relationship flowchart at the start of this arc only makes the teasing more obvious. However it should also be noted that the (stock blue) line connecting Ash to Serena is marked "Friend!"
She even seems to be getting romantic rivals. In XY026, Miette immediately picks up on Serena's interest in Ash and even goes so far as saying that if Serena doesn't make her move soon, she may end up taking Ash away from Serena. It's notable that Serena doesn't deny her interest in Ash, so far the only girl to do so.
In XY031, the gang, including Korrina and her Lucario, poses for a photo. Serena and Ash are standing next to each other, with Serena sliding closer to him just before the picture is taken. Rather obviously too, as Bonnie notices it (but not Ash, of course). A little later, when everyone has gotten their copy of the photograph, Serena looks at it dreamily, until Ash calls her to hurry and she turns around with a blush on her face.
The Sinnoh arc pairs Ash with Paul, who is everything that Ash is not, including cold, cunning, and mean to his Pokemon. This causes enough confrontations for the Fangirls to flock to the pairing, claiming Paul's only a jerk because he wants Ash.
Also in Best Wishes, there was some shipping between Ash and Trip going on. Trip seems to have the same personality like Paul...until BW022 when you realize he's a full blown Ice King but this attitude is limited to Ash only. In that episode the minute Ash tries to praise him, Trip avoids eye contact which is a huge sign of Sugar And Ice. Later appearances drop the Jerkass side completely.note Though that could be due to the sequel games upsetting the apple cart as much as anything. And when does any of Ash's rivals actually help him out concerning one of his Pokemon? Trip would be the first if you don't count Gary after he Took a Level in Kindness.
This scene, where Seymour hugs Ash for saving him.
Though she didn't pursue Ash further, Melody in the second movie has an interesting distinction: she was one of the only two beings that have kissed Ash prior to the X and Y saga.
Angie from Solaceon Town is often mentioned as much as any female companion in the race for Ash's heart.
The fact that James' sadistic fiancé Jessiebelle (the reason he ran away from home in the first place) is practically an Identical Stranger to Jessie is often taken as "smoking gun" evidence. (James sees Jessie as a substitute for someone he was supposed to marry, but was afraid to.)
Other Heterosexual Human Shippings
One episode preview for Pokémon threw up a storm in the shipping fandom by focusing almost entirely on a romantic scene between Tracey and Misty, despite the latter's long-established crush on the protagonist (and the fact that Tracey was a total Shipper on Deck for Ash and Misty back when he traveled with them). As it happened, the whole scene was just made up by one of Misty's sisters who thought that Tracey would make a handsome prince for her upcoming water ballet. Then they did it again in the preview for the next episode both characters appeared in. This time was a blushing scene that turned out to just be over a photograph of the whole group in Team Rocket's latest scheme. It didn't help that Misty was holding her new baby Pokémon that she had received from Tracey.
May and Drew have their moments. Plenty of them.
Giving May a rose ends up being something Drew does in nearly every episode he appears in, with the excuse of it being for her Beautifly, not her. Mean? Yes. Complete ship tease? Also yes. By the Battle Frontier episodes, he drops the excuse, knowing it fools nobody anymore.
Their other Contest rivals, Solidad and Harley, also assume there's something going on between them. Solidad also mentions that May is the only person Drew ever talks about anymore.
Cilan and Burgundy. Burgundy is incredibly obsessive over Cilan for beating her in a Gym battle. In her later appearances, she's rather kind and civil to everyone (people and Pokemon alike) except him. And in the Club Battle arc, she and Cilan actually put aside their differences and did a Team Rocket Motto-esque sequence together! It was kind of competitive between themselves, but so was the song between Annie Oakley and Frank Butler. She's clearly a tsundere.
Dawn was a Gary Fangirl and he didn't seem to mind.
There were Reggie/Maylene moments, too; in stark contrast to Paul's treatment of her.
Conway is seen Stalking Dawn in about every episode he's in.
Gardenia may have had a crush on James. She traveled to check up on his grass-types.
Bianca and Stephan in the Clubsplosion. The former constantly touches and plays with the latter's and his Sawk's muscles.
In the same vein, Bianca and Virgil in the Vertress Conference. From giving ice cream to him and his Eevee to wanting to give him a special prize for winning, it's clearly evident there's something going on.
While many of Pokémon's pairings are full of shiptease, Appealshipping (Zoey/Dawn) takes the cake. Their scenes together are just tinged with touchy-feely-blushy moments.
It doesn't help how hard Dawn took Zoey's words to heart.
Even before Zoey appeared in an episode, the pairing had tons of fans.
Morty spends nearly all of For Ho-Oh the Bells Toll withdrawn and sullen. Bear in mind that in previous episodes he was outgoing and happy. The target of his attitude switch is his friend Eusine, who's shown up with a Suicune fixation and a bad temper, leading many in the fandom to believe that the two have an unresolved past relationship. Also bear in mind that Eusine's subsequent Legend of Thunder appearance has him in turn being upbeat and caring, so it may be a two-way street.
Also, Iris and her rival Georgia. Their heated rivalry confrontations frequently feature them veryphysicallyclose toone another. There was also that instance where Luke's Zorua transforms into Georgia and Iris proceeds to touch it all over in order to use it like a puppet to mock Georgia. After Georgia Took a Level in Kindness, this pairing is much more evident.
Then there's Bianca who has no sense of personal space towards Georgia.
Volkner and Flint are really close.
Various Pairings involving Pokemon
Ash and Latias from the Pokémon Heroes movie. Latias has been openly crushing on Ash, in both human and Pokemon form. She's also the other of the two beings that have kissed Ash prior to the X and Y saga.
Chikorita also seemed to have a pretty big crush on Ash during the Johto arc.
Conversely, Dawn's Buneary had a crush on Pikachu, showing attraction and shyness often. And, from Pikachu's reaction during Dawn's visit to Unova, there's a chance that it's mutual.note Bonus in that they share a breeding group. A Thunderbolting Buneary, anyone?
Ruby and Sapphire are the closest thing any of the adaptations has to an Official Couple among main characters. They got along well as youngsters and adopted complete personality shifts after a traumatic incident involving a Salamence. Sapphire still loves Ruby, and Ruby still loves Sapphire, but Ruby's too shaken by all that has gone on in their lives to admit this even to himself.
Wallace and Winnoa are essentially an older Ruby and Sapphire, except that instead of running afoul of a Salamence, they had authority issues.note Wallace stepped down from his station as Champion just to be with Winnoa who was merely Senior Gym Leader (even demoting himself below her) but the whole arrangement just plain stressed Winnoa out enough to turn her off.
Platinum, Diamond, and Pearl are so close that it goes beyondTrue Companions and all the way to One True Threesome. A scene where they have to embark on separate tasks is essentially a tearful goodbye.
Then we have Black and White. White thinks Black is attractive early on, Black is often protective of White, and the two have had a Train-Station Goodbye as White was going off to train to stop Team Plasma.