We have developed a one-pot O-sulfinative Passerini/oxidation reaction, in which a combination of an aldehyde, an isocyanide, and a sulfinic acid react, followed by the addition of mCPBA as an oxidant to give the corresponding α-(sulfonyloxy)amides in high yields. This reaction is the first reported demonstration of an isocyanide-based multicomponent reaction using a sulfinic acid in place of a carboxylic acid. A wide range of aldehydes and isocyanides are applicable to this reaction.