Light irradiation can initiate the reaction while avoiding exerting additional physical effects on the monomer crystal. It can be used in topochemical polymerization based on free radical mechanism such as 1,4-polymerization of diacetylene or diene polymerization. UV light is widely used as initiation method as it does in conventional polymerization. In some circumstances, however, the polymerization initiated by UV light is so slow that unbalanced pressure will accumulate more easily as previously stated. γ-irradiation can trigger the reaction faster due to the shorter wavelength. Thus, it was proved to be a better choice than UV in various reactions such as topochemical polymerization of 1,3-diene carboxylic acid derivatives.