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.
Extremely common in shipping fanfiction and fan-art.
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 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).