Palladium-catalysed cross-coupling of aminals with N-sulfonyl hydrazones has been established via C–N bond activation under base-free conditions, in which one C–C bond and one C–S bond were simultaneously generated. It was successfully applied in the construction of a variety of aminomethyl substituted allylic sulfones. Preliminary mechanistic studies indicated that the unique electrophilic cyclopalladated complex was involved in the catalytic cycle.