In recent years, lacquer chemistry stimulated more attention from the scientific community due to its environmental friendly applications. Additionally, the “laccol” possesses promising radiation resistance due to its highly crosslinked polymer network. In nature, lacquer polymerization is induced via enzymatic radical initiation. Herein, as a novel approach, lacquer polymer was synthesized via cationic polymerization with aluminum chloride‐ethyl acetate coinitiator. This approach was further improved by polymerizing copolymers of laccol and styrene designed for use in radiation‐hard materials. The infrared spectroscopic data clearly provide evidence for reactions with trans conjugated double bonds present in long side chain (988 and 966 cm−1 are bending vibrations of conjugated alkenes) of laccol monomer accompanying polymerization. This was further verified with proton nuclear magnetic resonance analysis. An increase in hardness was observed for all the compositions: remarkably for neat laccol polymer, and 90% and 70% laccol‐styrene copolymers after the gamma irradiation using Co‐60 gamma irradiator. Properties such as thermal stability and hardness were improved after irradiation due to the increase in physical and small amounts of chemical crosslinking. Therefore, the developed materials are suitable candidates to produce radiation‐hard polymer and copolymer coatings for aerospace operations, nuclear reactors, and medicinal and automobile sectors. POLYM. ENG. SCI., 59:1611–1623 2019. © 2019 Society of Plastics Engineers