Transition-metal-free, sulfur-mediated allylic C-H arylation, epoxidation, and aziridination were realized through one-pot procedures. The reaction design involved initial addition between olefins and triflic anhydride activated sulfoxides, followed by subsequent reactions of the allylic sulfur ylides generated under basic conditions with arylboronic acids, aldehydes, or aldimines, to give allylic arylation, epoxidation, or aziridination products, respectively.