A series of epoxidized 1,2‐polybutadienes with various degrees of epoxidation are synthesized by the reaction of 1,2‐polybutadienes and m‐chloroperbenzoic acid. Additionally, the curing behavior of epoxidized 1,2‐polybutadienes with a cationic initiator and the relationship between epoxidation ratios and the dielectric, thermal, and mechanical properties of the cured materials are examined.