We report a wavelength-selective polymerization process controlled by visible/UV light, whereby a base is generated for anion-mediated thiol-Michael polymerization reaction upon exposure at one wavelength (400-500 nm), while radicals are subsequently generated for a second stage radical polymerization at a second, independent wavelength (365 nm). Dual wavelength, light controlled sequential polymerization not only provides a relatively soft intermediate polymer that facilitates optimum processing and modification under visible light exposure but also enables a highly cross-linked, rigid final material after the UV-induced second stage radical polymerization. A photobase generator, NPPOC-TMG, and a photo-radical initiator, Irgacure 2959, were selected as the appropriate initiator pair for sequential thiol-Michael polymerization and acrylate homopolymerization. FT-IR and rheological tests were utilized to monitor the dual cure photo polymerization process, and mechanical performance of the polymer was characterized at each distinct stage by dynamic mechanical analysis (DMA). By demonstrating complete light control in another sequential polymerization system (thiol-Michael and thiol-ene hybrid polymerization), this initiator pair exhibits great potential to regulate many other coupled anion and radical hybrid polymerizations in both a sequential and controllable manner.