A transition-metal-free protocol for the synthesis of non-terminal alkenylethers, alkenylsulfides, and N-vinylazoles fromarylaldehydes or diarylketones, DMSO and O, S, N-nucleophiles has been reported. In this protocol, 24 examples of non-terminal alkenylethers and 28 examples of non-terminal alkenylsulfides in 72–95% yields have been synthesized within 5 min. Moreover, 27 examples of non-terminal