The design and production of materials with excellent mechanical properties and biodegradability face significant challenges. Poly (butylene terephthalate-co-caprolactone) copolyesters (PBTCL) is obtained by modifying the engineering plastic polybutylene terephthalate (PBT) with a simple one-pot process using readily biodegradable ε-caprolactone (ε-CL). The material has mechanical properties comparable to those of commercial biodegradable copolyester PBAT. Besides, this copolyester exhibited remarkable degradability in natural environments such as soil and ocean, for example, PBTCL1.91 lost >40 % of its weight after 6 months of immersion in the Bohai Sea. The effect and diversity of specific microorganisms acting on degradation in the ocean were analyzed by 16 s rDNA gene sequencing. Theoretical calculations such as Fukui function and DFT, and experimental studies on water-soluble intermediates and residual matrixes produced after degradation, confirmed that the insertion CL units not only act as active sites themselves susceptible to hydrolysis reactions, but also promote the reactivity of ester bonds between aromatic segments. This work provides insight for the development of novel materials with high performance and environmental degradability.