Sulfonamides are important structures in pharmaceuticals, agrochemicals, and organocatalysts, yet the rapid and benign synthesis of these compounds is still a great challenge. Herein we report a photoinduced method for synthesizing sulfonamides from (hetero)aryl carboxylic acid oxime esters. This reaction proceeds via one-pot cascade radical−radical crosscoupling by energy-transfer-mediated photocatalysis. A wide substrate scope including (hetero)aryl substrates and late-stage modification of pharmaceutical molecular entities reveal its generality.