In Tales of Monkey Island, there is a chili pepper so hot, you can't touch it with your bare hands without getting burnt. You have to hold it to your tongue for eleven seconds.
World of Warcraft has (sadly outdated) Dragon Chili, made from mystery meat and a small flame sac taken from baby dragon bodies. Every so often after eating it, the character will breathe a damaging cone of fire on anything they're fighting.
The Jaba˝ero pepper in Kingdom of Loathing is evidently so spicy that "Just thinking about it makes your mouth hurt." Putting one in a spicy enchanted bean burrito, then eating one, gives one the (fairly useful) skill 'Chronic Indigestion'.
Joe And Mac: Caveman Ninja includes a jalape˝o pepper as a food item. Eating it provides invincibility and a fire attack against enemies, as well as a humorous animation with Joe or Mac breathing fire.
The RoguelikeOmega has a szechuan pepper as a findable item. If you eat it, "your sinuses melt and run out of your ears"— and you become immune to Sleep spells.
In Persona 4 Rise likes to put overwhelming amounts of spice in her food; one bite was enough to cause poor Yukiko to pass out.
Some servers in Space Station 13 let you create ghostlier chilis, a chili pepper hot enough to make whoever's foolish enough to eat one burst into flames. If the botanist making one gets it just right, it can turn people to ash in a single bite.