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“Chilli” is indeed the British way of spelling it, and is used in the UK and its former colonies. Here in the U.S., “chili” and “chile” are both used, although periodicals nowadays use “chile” as the preferred spelling to refer to the pepper, and to distinguish it from “Chili,” the dish with ground meat and beans.

For etymology buffs, “chile” is not from Spanish spoken in Spain. The word is derived from Nahuatl, the language of the Aztecs. Dialects of Nahuatl are still spoken in parts of central Mexico, and a lot of words in Mexican Spanish are “hispanized” versions of Nahuatl words, like “papalote” (kite), “guajolote” (turkey–“pavo” in other countries), “tlapalería” (hardware store). “Chile” is used more in Mexico & Central America, and the plant is, indeed, native to the Americas. In South America, hot peppers are called “ají,” as in “ají amarillo” used by Peruvians. And the Filipino word “sili,” as we know, comes from “chile,” and was most likely introduced by soldiers brought over by Spain from Mexico.