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We have a few chilli pepper plants (I'm afraid I don't know what kind as the seed packet was unfortunately lost) but I don't know when the best time is to pick them so that they will be as spicy as possible.

I know from this question that all peppers start green and should eventually turn red and that the flavor will be better the longer I leave it but I haven't found much information about spiciness. (Certainly nothing cited.)

There is some debate over whether green or red peppers are hotter and I know that smaller chillies tend to be hotter but I assume that is according to ripened size rather than that an immature pepper will be hotter than a fully grown one.

When can I best harvest the peppers?

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    Generally the maximum amount of accumulated capsaicin within the fruit will be found in a fully ripe fruit. They don't necessarily taste hotter, though, because of the offsetting by the distinct increase of sugar as the fruit ripens.
    – J. Musser
    Commented Sep 19, 2014 at 18:23

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Red peppers are usually considered hotter, but sweeter, than green fruits. Here is a thread where everyone agrees on that point. But the heat level often goes along with the stress level of the plant. most of the people on this thread also think red is hotter. If you water only minimally, grow the plant in scorching sun, and are skimpy on the fertilizer, you will end up with some very hot peppers.

This article even says that fruit can get hotter after picking, even when green. Therefore you can choose peppers to use according to the heat needs of the food you are making. Here is a good paragraph to go along with that:

Yes, red jalapeno are hotter than green. Jalapeno chilies progressively get hotter the older they get, eventually turning bright red. As they age, they develop white lines and flecks, like stretch marks running in the direction of the length of the pepper. The smoother the pepper, the younger, and milder it is. The more white lines, the older and hotter. Red jalapeños can be pretty hot, if they have a lot of striations, but they are also sweeter.

And I just found what you could consider almost a duplicate of this post, over on cooking.stackexchange.com:

Are chillies hotter when they're ripe?

The answers to that question correlate to this one, agreeing that the red ones are hotter.

So I would wait until the peppers have colored fully, if you want the most heat possible. The longer you leave them on the plant, the hotter they'll get.

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    I agree with the plant stress - heat correlation comment. I've always found that alternately watering and letting plants wilt a bit produces peppers significantly hotter than by maintaining continual moisture. I've seen this in cayenne, jalapeno, and Rocoto/Locoto.
    – That Idiot
    Commented Sep 23, 2014 at 15:24

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