Azide functionalities have been studied for various applications, since azide groups may generate reactive nitrene intermediates thermally and/or photochemically to mediate C-H insertion reaction of arganic compounds. In this study, azidoformate and sulfonyl azide groups were adopted for the vulcanization of styrene-butadiene rubber [SER]. Crosslinking behaviors of SBR with the azide compounds were investigated, along with mechanical and rheological investigations on the resulting SBR. The SBR exhibited interesting characteristics compared with those of SBR vulcanized with traditional radical-mediated peroxide crosslinking systems, demonstration the potential of non-catalytic C-H insertion reaction technology for polymer modification.