An efficient method for phosphine-catalyzed sulfophosphinoylation of α,β-unsaturated ketones for synthesis allylic organophosphorus compounds has been reported, in which α,β-unsaturated compounds acting as zwitterions react with electrophiles and nucleophiles to form a C-P bond and a C-O bond and obtain allylic organophosphorus with high regio- and stereoselectivity in moderate to excellent yields.