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This answer might vary between types of chillies, but I'm curious to know when they're hottest.

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4 Answers 4

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McGee writes: "Capsaicin appears to accumulate in the fruit concurrently with the pigment during ripening". (On Food and Cooking, p.212)

So yes, chilis get hotter as they ripen (that is, as they turn from green to red). Many chili varieties are picked and sold in stores while still unripe and green (e.g. jalapeño, serrano, poblano), but you will occasionally see ripe, red ones in stores.

All of the dried chilis I've seen in stores have been completely ripened before drying (e.g. chipotles, which are smoked, dried red jalapeños and anchos, which are dried, red poblano peppers).

I've personally observed this effect with padron peppers, which are usually picked green and mild, but can ripen to red, hot peppers if left on the plant.

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Not really. The chemical that gives chillies their heat is called capsaicin. It is an extremely stable alkaloid, and so remains potent even after a long period of time: note, for example that dried chillies and even chilli flakes are still hot.

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Since the capsaicin is mostly concentrated in the placenta wouldn't there be more of it at the point of ripeness, thereby making it "hotter"? –  Cos Callis May 6 '12 at 14:11
    
The placenta doesn't disappear per se, I imagine it just dries out. That means there's less water, but the amount of capsaicin shouldn't change all that much. –  ElendilTheTall May 6 '12 at 15:00
    
For my part, I'm not really talking about "after ripeness" (loosing potency) as perhaps "before ripeness". Wouldn't the capsiacian build up on the way to ripeness? Such that if you harvest the pepper too soon it would be less potency? –  Cos Callis May 6 '12 at 17:46
    
Yes, I suppose so. I'm coming from the angle of buying chillies at the supermarket, where they are obviously always ripe. –  ElendilTheTall May 6 '12 at 17:56
    
I'm also looking at it from a post-pick point of view. Their heat may well build as they grow and ripen, but I would think it plateaus at a certain point. –  ElendilTheTall May 6 '12 at 19:22

I know this is an old post, but had to reply. I grew jalapenos this year, and the heat difference between green and fully-ripened red is astounding. The green jalapenos had a very, well, green flavor like that of a green bell pepper, but with a mild heat.

After reading a lot of posts around the web, that almost all seem to say that peppers get "smoother" as they ripen, I interpreted that as meaning that the heat wouldn't increase. My interpretation was faulty! The red, ripened pepper was many, many times hotter than the green. I wasn't expecting that burst of flavor when I popped a slice of pepper in my mouth to experience the "smoothness" of the ripe pepper!

I can't tell you the science behind it, but I can verify that, at least in my garden and with my jalapenos, the ripe peppers are far hotter than the green.

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This is my experience, too. There's some sweetness to balance out the heat, but they're definately hotter. –  Joe Sep 4 at 15:37

Most chiles become more picante as they ripen. But they also become much sweeter. Jalapenos are a good example. Red jalapenos are much more delicious than green ones. Most of the 'heat' is in the seeds and the tissue connecting the seeds to the capsule. You can pare those parts out with a small knife. I eat most of my ripe jalapenos right in the garden, pocket knife in hand!

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