Photopolymerization of crystalline-state monomers belongs to the field of photopolymerization methods, and the invention discloses a novel photopolymerization method. The method breaks through the traditional concept that the photopolymerization can only be performed from a liquid state to a solid state and proves that the photopolymerization reaction can also be performed on solid-state monomers for generating a polymer. As the structure of the crystalline-state monomers is compact and regular and the formed polymer is similar to the structure of the monomers, the volume shrinkage of the crystalline-state photopolymerization can be reduced. According to the method, long chain (methyl) acrylate type, vinyl ester type and vinyl ether type monomers are of crystals at the polymerization temperature, and the comb-shaped polymer which is formed after polymerization is also crystalline. The volume shrinkage during the polymerization process is smaller than that of liquid-state polymerization. The new method introduced by the invention can be tried on the photopolymerization of other monomers, and a new field is created for the photopolymerization. The volume shrinkage during the polymerization process is smaller, and the method can be widely applied to low-temperature photoetching, patterning and other aspects.