A facile and novel N-heteroarenium iodide-catalyzed hydroalkoxylation of enamides has been described. The protocol provides easy access to N,O-acetals, which proved to be a versatile synthetic synthon. The hydrosulfonylation, hydroamination, and hydrophosphorylation products of enamide could be indirectly provided from N,O-acetals. The reaction mechanism was further investigated, which indicated that the hydroalkoxylation of enamides was driven by weak coordination between enamide and the contact ion pair of N-heteroarenium iodide.