The　ring　opening　copolymerization　(ROCOP)　of　epoxides　and　cyclic　anhydrides　is　one　of　the　most　important　ways　to　synthesize　polyesters　both　in　industrial　and　academic　fields.　Herein,　the　zeolitic　imidazolate　framework-67　(ZIF-67)　was　used　as　a　heterogeneous　catalyst　for　the　ROCOP　of　epoxides　and　cyclic　anhydrides　without　co-catalyst　and　initiator.　Notably,　the　obtained　polyesters　with　alternate　structures　were　proved　by　the　1H　NMR　spectrum　and　FTIR　spectrum,　which　indicate　the　ROCOP　is　alternatively　copolymerized.　Kinetic　study　of　the　ROCOP　of　cyclohexene　oxide　(CHO)　and　phthalic　anhydride　(PA)　shows　that　the　polymerization　reaction　is　first-order　kinetics.　The　apparent　activation　energy　(Ea)　of　the　ROCOP　of　CHO　and　PA　catalyzed　by　ZIF-67　was　found　to　be　about　104.4　KJ/mol.　A　possible　mechanism　of　ROCOP　of　CHO　and　PA　is　that　the　metal　Co　coordinates　with　the　oxygen　atom　on　the　monomer　to　weaken　the　C-O　bond　thereby　opening　the　ring　structure　and　initiating　the　copolymerization　reaction.　In　this　study, a　new　system　for　the　copolymerization　of　epoxide　and　anhydride　catalyzed　by　heterogeneous　catalysts　was　discovered,　which　has　important　guiding　significance.　©　2024　John　Wiley　&　Sons　Ltd.