Chili peppers are native to the Americas and only reached India after European contact.
Chili peppers were domesticated in Mexico thousands of years ago and were entirely unknown outside the Americas until Christopher Columbus’s voyages opened contact between the hemispheres in the 1490s. Spanish and Portuguese traders carried chili seeds back across the Atlantic and then onward along their trade routes into Africa and Asia.
Portuguese traders introduced chilies to India through their coastal colonies, such as Goa, in the 16th century. The peppers spread rapidly across the subcontinent and were adopted so thoroughly into regional cuisines that they now feel inseparable from Indian food, even though black pepper, not chili, was the dominant heat source in Indian cooking before that point.