A thiol monomer is shown to copolymerize with vinyl ether, allyl, acrylate, methacrylate, and vinylbenzene monomers. These thiol−ene polymerizations are photoinitiated without the use of photoinitiator molecules. It is seen that the polymerization proceeds more readily when initiatorless samples are irradiated with light centered around 254 nm as compared to 365 nm light. To demonstrate resistance to oxygen inhibition, thin polymer films of 3−15 μm are polymerized while exposed to ambient air. Without photoinitiator molecules present, light is attenuated only by the monomer and polymer. This feature leads to greater penetration of ultraviolet light and allows for the polymerization of extremely thick polymers. Thick cures of up to 25 in. are obtained using a thiol−vinyl ether system.