We report the formation of zinc reagents by the reaction of styrylsulfonium salts with zinc powder. Transition metals and other additives are not required for promoting zincation. Zincation tolerates a variety of sensitive functional groups, including esters, bromides, and boronic esters, and proceeds with complete retention of stereochemistry. This method presents a practical approach to the formation of zinc reagents that can be used in a variety of functionalizations, such as halogenation, carboxylation, and Negishi cross-couplings.