Kim, Ron, Shego, and Senor Senior Jr. are of the most Genre Savvy. This however doesn't prevent them from falling victim to Genre Tropes (or that they fall into the tropes as part of a fourth wall bending realisation that they have to do so to have a story), but does make for some great Lampshade Hanging afterwards.
Señor Senior Sr plays this totally straight, because he learned how to be a supervillain from books and it's an eccentric hobby for him.
Flash occasionally shows traits of this, as this quote from "The Brave and the Bold" demonstrates:
Flash: Usually when it's this empty, flesh eating zombies show up. Green Lantern:You watch too many horror movies... (interrupted by the sound of a brainwashed mob) Flash: Maybe you don't watch enough.
After Gorilla Grodd subdues and imprisons the Justice League, Clayface says they should just kill them off now—having acted in enough movies, Clayface knows that saving them for the showy public execution Grodd wants will give them time to escape, no matter how helpless they seem. Hilariously, this is actually J'onn, apparently making sure not to slip up anywhere in his act.
Legion of Super Heroes: Bouncing Boy is the 21st Century horror movie aficionado, so he warns them of the rules.
The Venture Bros. has # 21 and # 24 . In "The Lepidopterists", they are well aware that they posses the perfect combination of "expendable and invulnerable". Upon being sent off on a mission with # 1, they remark that his cool professionalism marks him for death, while their bumbling incompetence will see them through to the end. Later, when they point out that # 1's lack of a name makes him a Red Shirt, he reveals his name, only to have it dismissed as a device to make his impending death more emotional. Ultimately, he meets his fate when his impressive escape techniques draw the attention of Brock Sampson. # 21 and # 24 were pretending to be wax sculptures at the time. Ironically, or at least in a cruel twist of fate, in the season 3 finale, 24 stands near the Monarch's car when it suddenly explodes. He's killed in the blast as 21 unintentionally catches his burning head.
Lisa: This broom closet is not what it seems. It's a secret surveillance room guarded by a tiny evil robot! Homer: Ugh. Is this gonna be like one of those horror movies where we open the door and everything's normal and we think you're crazy, but then there really is a killer robot and the next morning you find me impaled on a weather vane? Is that what this is, Lisa?
When Sierra drops her Obfuscating Stupidity in the confessional, she's revealed to be having this in spades, up to intending to manipulate Heather; all due to her being an Fangirl that watched the show obsessively.
Played for Laughs in Johnny Test, "When did we land in a bad decade genre medium?" is a running gag, e.g. "When did we land in a bad 70s cop show?"
Ren from The Ren & Stimpy Show has shades of this, particularly in the episode "A Yard Too Far". The eponymous duo is starving as they suddenly sense a delicious smell from someone's backyard.
Ren: Wait a minute! I'm not stupid. I've seen cartoons like this before! If I set foot into this yard, I'll probably get ripped into shreds by some enormous dog!
This is parodied shortly after when Stimpy tells Ren there is no dog only for Ren to attacked by a killer, psychotic baboon.
Roger from American Dad! is pretty Genre Savvy. In one early episode he joins a car dealership:
Roger: Oh, it's like a sitcom come true! I'm part of a workplace ensemble! He must be the sarcastic guy. And he's the dumb guy. Oh! He must be the black guy who doesn't talk! *said guy glares at him* Yessss!!
In "Legend of the Gobblewonker", Dipper brings seventeen disposable cameras along with him to search for the Gobblewonker, since he realizes how often camera problems ruin monster hunts in movies. Also, Soos worries that he might just be a "side character" and get killed off. Ironically for Dipper, allof his cameras get destroyed before the monster shows up.
Animaniacs: Slappy Squirrel used to star in slapstick cartoons and has Medium Awareness, so she knows all of the classic cartoon tricks and gags. Because of this, any attempts to use these tricks against her tend to fail horribly, as she sees them coming from a mile away and knows how to thwart them.