The Social Expert is the most likely one on this list to exploit their social skills for their own purpose but also to support the team's purpose.
Not to be confused with Face. Also not The Face Of The Band, though the roles can overlap. The name comes from the tradition of Dungeons & Dragons where a character in a Player Party would be the face of the group: they have stats and skill sets based on talking and resolving conflicts without fighting.
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Anime & Manga
Cardcaptor Sakura: Tomoyo interacts with everyone and contrasts them with her Muggleness. She's also emotional support for Sakura, and Syaoran too after he calms down.
Witch Hunter Robin: Chief Inspector Shintar Kosaka represents the STNJ to other organizatons and passes on the office's reports to the parent organization, SOLOMON. He has a lot of friends in the police department and all he has to do is call one of them to get info on suspects.
Baccano!: Luck does most of the talking and business for the Gandor family. His friendship with Firo is also the reason the Gandors have a good relationship with the Martillo Family. His brothers are either too quiet or too aggressive for such a responsibility.
Crest of the Stars deconstructs this trope with how Jinto feels about being forced into this role. Because he seems to get along with everyone (perhaps because he wasn't born into Abh society like everyone else) he has to act as a go-between both inside the Basroil's crew and with other soldiers. This means shouldering everyone's emotional baggage and translating for the one receiving the message.
Code Geass: Kaguya invokes the trope in her bid for Zero's hand in marriage. "You'll need a public face, right?"
Rock from Black Lagoon. He isn't much for violence like Revy and Dutch are, but he makes up for it by being the Lagoon Company's negotiator. He's also the most idealistic of the crew.
Archie Comics: Veronica Lodge. She's The Chick and her skills are mostly social instead of practical, but she contributes by being the only one with unlimited wealth and resources.
Among not just the Batfamily, but the entire DCU, Nightwing. He is friends with every hero in the universe, able to call on help from anyone from the Justice League, Teen Titans, and anyone else who knows him, even those on Oa and in Hell. He's even teamed up with his enemies, just because he asked nicely.
Superman is this in the Justice League as highlighted in Grant Morrison's JLA: New World Order. After The Team realizes that fire is the key to defeating the Martians, he makes a TV announcement telling the people of Earth to all light matches, cigarette lighters, etc.
The Invisible Boy is more or less a Tagalong Kid and until the climax his only contribution is networking and idealism.
Loki was the face of Thor's group of warriors before his Face-Heel Turn. The others remark on his silver tongue and he's the one who did the talking in Laufey's court.
Maddie Bowen in Blood Diamond is able to help negotiate everyone through situations that would require a lot of risky trickery. This includes pretending to interview a soldier guarding equipment so Danny can sneak behind him, and stopping a group of bandits simply by asking them if they'd like their pictures taken. Fridge Brilliance says she would be expected to have some PR skills as a journalist.
Haruhi herself; always out to promote the SOS Brigade and Kyon notes that she 'knows how to get answers' peacefully from the apartment keeper during the investigation of Asakura's disapperance. In practice the trope is inverted as she either steamrolls people with blackmail or her personality if she's not outright ignoring them.
Sir Dinadin from Camelot's Round Table. He doesn't like fighting and thinks Courtly Love is a waste of time. The other things he's noted for is good humor and being more sociable than his fellows: he's the only one that can recognize all of them by their face in addition to their shield crest. This ability is naturally helpful for knights who otherwise might not recognize their own king.
Dolores Umbridge exploited this trope in Harry Potter and the Order of the Phoenix. She doesn't want Hogwarts students trained in offensive magic so she fills the Defense Against the Dark Arts class with lessons like 'negiotation' and 'non-retaliation' on the premise that these skills are just as important for future Auror teams as curses and counter-curses. While this might not sound like a bad idea, the fact that she is imposing these restrictions while a wizarding civil war is brewing in the background make it clear that, in this case, being The Face is less useful than knowing how to defend yourself from homicidal lunatics. It's also clear from what happens a couple of books later that she's deliberately watering down the students' skill-set so that they'll be less of a threat to face when there's a coup.
Hermione Granger frequently acts as such, which comes in handy when dealing with older and arrogant wizards since she is also The Smart Guy.
Strickland is this in Kill Decision, though he becomes painfully aware that he doesn't have the same tech-savvy as the rest of his team.
Perhaps unsurprisingly, Garik "Face" Loran of Wraith Squadron serves as the squad's general-purpose fast-talker and people person. Even when he becomes The Captain, he prefers to handle things like recruitment and dealing with bystanders himself.
Live Action TV
House - Cameron is The Heart variety. She goes out of her way to 'get to know' the patients, as opposed to the other members of her department who more or less don't care and only ask for diagonistic information.
Mystic Knights Of Tir Na Nog: Deirdre is the only female of five knights, and also the only one to regularly do more than fight. When making alliances who is the local head man going to listen to: The thief, the druid apprentice, the princes from the Land of Never-Heard-Of-It, or the local princess?
NCIS Abby, though crossed with The Smart Guy, is the cutie who interacts with all four of Gibbs' group.
The IT Crowd: Jen is the socially capable Nerd Nanny for the IT Department. She has no computer skills but, unlike the rest of the cast, she has social skills.
Firefly. Officially, Inara's role on the ship is to use her social contacts to "open doors that would otherwise be closed" to a group like Captain Mal and the crew.
Jayne, but in a different way. His official job title on the ship is "Public Relations" and considering the Serenity's relations with the public this usually means hurting people.
Simon's knowledge of the Alliance, politeness, and ability to be diplomatic also count.
Dennis from It's Always Sunny in Philadelphia is this, relative to the rest of the group. He frequently proves himself to be the only member of the group who can function in certain social situations, though he is hardly a social person.
Buffy the Vampire Slayer: Xander is The Heart and lacks the supernatural powers of his teammates, but is best friends with Buffy and Willow to the end. His storylines tends to revolve around interpersonal relationships, and, as the most consistent of the Scooby Gang, he interacts with everyone.
The Big Bang Theory: Besides being the only female lead, Penny is the only one of the five who is not a socially incompetent nerd.
Community: reluctant Team Dad Jeff Winger tends to be saddled with whatever talking and negotiating needs to be done since he's a former lawyer who's skilled at coming up with awesome speeches off the cuff.
Subverts this trope with Xander, who thinks of himself as The Charmer. "Plan Xander" never works and the Rangers have to bust out the weapons.
Madison has more success but doesn't feel any better about it.
Power Rangers RPM: Ziggy can barely fight, but he gets along well with everyone; even forming his closest bonds with brooding rebel Dillon and, eventually, Broken Bird Dr. K.
In the game world of Level Up the Never Fail guild lets Wyat do all the talking with other players because he's The Charmer. In the real world, however, he's Adorkable and Lyle's the one with school-wide friends.
Sophie, the grifter from Leverage. She stands out as the stable and emotionally competent one of the group (though she does have her own issues), and her job goes beyond manipulation and grifting. She's usually the one next to Nate talking to the clients, and she's the one reassuring them, not just asking for the facts. When she leaves, each member of the team separately calls her for advice, either on how to deal with the con, or on personal issues.
"We trust Nate to run the con. We trust you to keep us safe."
Carl is the liason of Special Unit 2 to the link underworld. He's not personable or friendly to say the least but he does have useful connections and considering other links want nothing to do with SU 2 he's a step up.
The core cast of Bones is four "Squints" and a smooth talking FBI agent. While the former collects and anaylzes evidence in private the latter's gathering information from people related to the Crime of the Week and interogating suspects.
The A-Team: Not surprisingly, Face fulfills this role by procuring rides and equipment for the team. You need a towtruck/limo/cab company? The Faceman can get that for you with some smooth moves and a silver tongue.
Leslie is this in Parks and Recreation, which is part of the reason why she takes on a leadership role, despite Ron technically being her boss. Leslie is almost always the one giving speeches and for good reason. If she delegates to Tom or Ron, the speeches are either shameless self-promotion (Tom) or blunt dismissals (Ron).
On Person of Interest Finch, lacking martial arts or gun play skills, frequently serves to socialize with whatever person he and Reese have to protect that episode.
In Primeval Jenny Lewis fills this role only in season 2. She is hired to act as the team's liason with the public and essentially come up with cover stories for them. She morphs into The Chick in season 3.
In most pop/rock bands, the lead singer is usually this.
In groups with multiple "lead" singers, the most commercially appealing (often the best looking) can be this.
In Dino Attack RPG, Dr. Wallace Breen is the Face of XERRD. Despite his scientist background, this was specifically the reason why Dr. Breen was recruited by Dr. Rex, since his true strength lay in his use of rhetoric and he had prior experience as a CEO and a politician.
In Dungeons & Dragons, (and by extension, all other RPGs) this character role is known as The Face. Also called "the party face". This is the character that handles the public relations for the party. They have skills in Diplomacy and/or Bluff, and only rarely in Sense Motive/Insight. Traditionally, bards, rogues, or paladins fit well in this role.
Shadowrun: Any character with a high Charisma and Social Skills like Etiquette, Interrogation, Leadership and Negotiation.
Earthdawn. Having a high Charisma is essential for each of the following.
The Troubador Discipline was good for this, with Talents like First Impression, Lasting Impression and Haggle.
Characters with other Disciplines can fill this role by choosing General Skills such as Acting, Bribery, Conversation, Engaging Banter, Etiquette, Fence, Flirting, Seduction, Streetwise and Trading.
Call of Cthulhu. The Field Manual of the Theron Marks Society (in the supplement Terror from the Stars) recommended having one of the PCs be a Communication Specialist - a charismatic character who is a good talker. They would have a high Appearance and high percentages in the skills Bargain, Credit Rating, Fast Talk and Persuade.
In Legend of the Five Rings Courtiers are explicitly designed to play this role, as even though most PCs should have basic social skills to survive Rokugan's complicated system of etiquette and conversation, it helps to have someone who can recruit allies and deal with gossip and slander. In a pinch, Air Shugenjas and more politically oriented Magistrates and Bushi (particularly from the Scorpion or Crane Clans) can fill this role.
In the BattleTech RPG one of the premade character archetypes is called the Faceman, basically a mix between a public relations manager and a lawyer, who works for a mercenary company. While he is next to useless in any fight it is mentioned that merc commands that don't have one of these guys usually go under within a year, often before seeing a single battle, thanks to legal, bureaucratic and monetary issues.
The Clans' merchant caste generally plays this role for the Clans who are willing to deal with the Inner Sphere. Merchants still see the Spheroids as destructive primitives but are able put this aside and hide their feelings during negotiations, unlike the other castes (especially the warriors), to score a good deal.
Champions. This type of character would have a high Presence score and skills based on that Characteristic, such as Acting, Bribery, Bureaucratics, Conversation, High Society, Interrogation, Oratory, Persuasion, Seduction, Streetwise and Trading.
Super Smash Bros.: in The Subspace Emissary Peach makes herself useful by breaking up fights and turning potential enemies into friends, mysteriously producing tea, in contrast with the Action Girls Samus and Sheik.
Emil from NieR, who is also The Heart and a Tagalong Kid, does what he can to keep an upbeat attitude and help his friends get along.
Stocke, the protagonist of Radiant Historia starts off as The Stoic, but also starts off with a growing circle of friends who he cares about dearly. He helps his party members through a variety of internal and external conflicts, and is always sensitive to their issues. And at one point, he helps his best friend Rosch and an NPC with relationship advice.
Varric Tethras in Dragon Age II and later installments. Keeping him in the active party lets you avoid several big fights by letting him take over the negotiations. And you know things are really bad where he decides to start shooting instead of trying to talk first.
Planescape: Torment You can build the Nameless One with high social scores and play him this way.
In Mass Effect 3, Commander Shepard essentially becomes this for the Alliance, which is lampshaded by Admiral Hackett.
The Order of the Stick has Elan the Bard whose highest stat is his charisma. In the first arc, this was invoked when Roy told Elan to convince a teen goblin to asssist them.
Jack once lampshaded the fact that the humans functioned as "Face Men" for the Autobots.
Captain Planet: Ma-Ti is the heart variety because no matter where they go he is instantly liked and can communicate to animals, knowing how they feel and asking for their help. Kawami, however, is usually the one ending group conflicts
Phineas and Ferb: Phineas is the one talking with who ever the group needs for their latest "Best day ever", from city officials to delivery guys to the Fireside Girls. The best example is persuading Love Handel to reunite for a concert while directing the girls to make a stage. He extra points for contrasting his brother Ferb, who rarely ever talks.
My Little Pony: Friendship Is Magic Fluttershy fills this role for the mane cast but only for non-ponies. Otherwise she's a Shrinking Violet. For example, in Dragonshy Twilight's plan for dealing with a dragon boils down to: 1.) Escort Fluttershy to the dragon's cave and 2.) Have her talk with it.
Applejack is this for the Apple Family in Ponyville due to Big Macintosh's quiet demeanor.
In Avatar: The Last Airbender , believe it or not, it's Toph. The youngest and yet the one with the most social savvy. Technically, being the Avatar, it should be Aang at the customs office and the Earth King's birthday etc but she's the one doing the talking. Even though she lived her life secluded and spoiled, without anyone even knowing that she exists.
Some would say that Anastas Mikoyan was the most likeable (and stable!) of Stalin's inner circle; a man who went for much more practical (and much less brutal) measures to revive Russia after the Civil War than Stalin. He was also seen as a fairly genteel "traveling salesman" by the West, in comparison to the bombast of those he answered to.