Love — even Puppy Love, perhaps especially Puppy Love — makes the young and innocent blush. Whether speaking of the Love Interest, realizing that you are the Love Interest, being caught studying the Love Interest (especially by that character), declaring that She Is Not My Girlfriend, or actually talking to the person, expect the character to turn red, still more so if the Love Interest expresses affection or praise. Very young or innocent characters may evince this even when an attractive member of the opposite sex seems to notice them, or when witness other characters in love. Less innocent ones may be driven to it only by the Love Confession. Because it is out of control, the Tsundere and those Oblivious to Love may be betrayed by it.
People prone to the Luminescent Blush or Blush Stickers are bound to suffer these. The Celibate Hero is often but not always prone to it. An apparently hard-bitten character who evinces it is revealing a soft side to himself. Adolescents are particularly prone to revealing they are not as grownup as they pose as.
Contrast Gibberish of Love, which indicates more ineptness than innocence.
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Anime and Manga
Hanaukyō Maid Tai La Verite episode "Forced Entry". When Ikuyo Suzuki teases Ryuuka about her feelings for Taro, Ryuuka blushes furiously while denying it.
Yamada, the main character of Kase-san, seems to have this going for her every other panel. Her love interest Kase, despite being considered cool and confident by most of the school, doesn't fare much better.
Card Captor Sakura features an interesting variant, where Tomoyo blushes at Sakura's older brother Touya. However, Touya isn't the object of her affection: Sakura is. Tomoyo's blush was because due to the shape of Touya's ears reminding her of Sakura's. It should also be noted that she tends to blush whenever she coerces Sakura into one of her many, many custom made costumes.
In Captain Britain, while he recounted some transdimensional adventures, he mentioned a woman. The children listening tease him about how he blushes.
On Minimonsters Frank Einstein blushes a lot when someone mentions his love for Henrietta, saying in denial "She Is Not My Girlfriend!". He also blushes when she is with him.
Used extensively by Kalash93 when he writes romance.
Extremely common in shipping fanfiction and fan-art.
Mushy, Romance-y Junk has this happen once or twice. If you're bored, take a shot each time Rancis or Vanellope does this, then immediately go see a doctor.
In Tangled, Pascal turns bright red both at the Near Kiss in the boat, and the actual kiss in the epilogue.
In Rick Riordan's The Son Of Neptune, when Ella returns with Tyson, she blushes when she talks to Percy of it. When Percy calls Tyson "you big charmer," Tyson blushes too.
Tales of Kolmar has Lanen, influenced by her father's demon-made attraction charm, fall for him complete with blushing at the very thought of him despite being in her twenties and, she thought, over that kind of reaction to boys. She didn't know he was her father then.
In P. G. Wodehouse's Jill The Reckless, a Flash Forward recounts how Otis would blush on his wedding.
In Wen Spencer's A Brother's Price, Jerin Whistler blushes profusely at thoughts of the Princess Ren, and especially at innuendo. He's blushy in general, once flushing after a bath is prepared for him because of the idea that strangers have paid that much attention to a place where he is to be naked.
In Poul Anderson's Virgin Planet, at the end, the two heroines decide to resolve the Love Triangle by rolling dice for who got the hero. He waits, and "had the grace to blush."
In Connie Willis's To Say Nothing of the Dog, when Verity tells Ned that he was so time-lagged he should have fallen in Love at First Sight with the first girl he saw, and Ned says that the first girl he saw was her, Ned thinks a proper Victorian maiden would have blushed. Verity is crisp and logical.
In L. Jagi Lamplighter's 'The Unexpected Enlightenment of Rachel Griffin, "My love" — which is a regional saying that means nothing — still turns Rachel's face hot enough to fry eggs on it.
In the Rune Factory games, when you court various women, some will show this blush when you talk to them, and your friendship level is high enough.
In Persona 4, the various romantic interests will sport one when you get to the last stages of their social links. It's noticeable, because you're "just" hanging out after school, something they acted perfectly casual about earlier in their social links. The blushes will (largely) disappear if you choose to stay friends instead of dating them, however.
In the spinoff Equestria Girls, Twilight Sparkle gets one every time Flash Sentry makes an appearance, though their relationship never goes further than that.
In the Batman: The Animated Series episode "The Cat and the Claw", Bruce Wayne meets Selina Kyle for the first time and blushes, even stumbling over his words a little speaking to her.
Korra does this rather a lot around Mako in Book One of The Legend of Korra; examples include after a Sleep Cute moment and during and following their first kiss in The Spirit of Competition. Interestingly, while Mako returns her affections, he has yet to display this trope in return, at least around Korra (though he did have awkwardness and blushing aplenty during his first encounter with his Romantic False Lead Asami).