I would advise against cornmeal - what you will end up with is chili polenta (ask me how I know :-) I use corn flour or masa to thicken my chili. And I add it in last, but while it's still cooking because you want it to cook as well. OH and make it into a slurry before you add it to avoid lumps!!
I use Bob's Red Mill fine ground cornmeal to thicken my slow cooker chili all the time. It doesn't take much, I usually use 1/4 cup to 5-6 qt chili. I've never ended up with chili polenta..thankfully. Maybe the long amount of slow cooker time prevents that particular catastrophe...or you used much more of it....like a box? Lol
Definitely add it now or you will end up with harsh and grainy chili. I suppose the exception to that would be if it's instant cornmeal, but I would add that at the beginning as well. You can also thicken it using a potato masher if there are beans in the recipe. I've also used refried beans from a can.
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