AbstractA kind of four‐functional epoxy resin containing tertiary ester groups (FETE) was designed and synthesized by two‐step reaction: first, the nucleophilic substitution reaction between linalool and isophthaloyl chloride, and then epoxidation. The chemical structure of obtained product was determined by infrared (IR) spectroscopy and nuclear magnetic resonance spectroscopy. Unlike traditional thermosetting epoxy resins, the cured FETE could degrade rapidly at low temperature (200–300°C). Dynamic mechanical analysis analysis showed that through copolymerization of FETE with (4,5‐epoxycyclohexane‐1,2‐dicarboxylic acid diglycidyl ester) epoxy resin (TDE‐85), the glass transition temperature (Tg) of copolymer system could be adjusted in the range of 136–179°C; FETE had good miscibility with TDE‐85. The thermal degradation behavior of the copolymer system was studied by theoretical calculation, thermogravimetric (TG), and TG coupled with FTIR analysis, the results showed the thermal decomposition performance of the copolymer system could be adjusted in the range of 200–400°C. The tertiary ester groups in FETE were easy to thermally degrade and caused the network skeleton of the copolymer system to collapse. The FETE would have good prospects in reworkable electronic packaging, recycling or degradable epoxy resin area.