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Poly(ε-caprolactone-co-trimethylene carbonate) (PCLTMC) is a biodegradable copolymer, which is widely used for medicine and tissue repair systems, and its morphology, degradation and mechanical properties have been extensively investigated. However, its crystallization behavior with different copolymerization ratios has not been studied systematically, which is of great significance for the study of property regulation and an understanding of the crystallization behavior of random copolymers. In this paper, the relationship between the crystallization temperature Tc, melting point temperature Tm and crystallinity Xc of copolymers with different molar ratios was determined by differential scanning calorimetry (DSC) using a non-isothermal crystallization method. The results show that the melting point and crystallinity of the copolymer decrease with an increase in TMC composition. The equilibrium melting point of the copolymers was predicted by an isothermal crystallization method, using the Hoffman–Weeks extrapolation method and crystallization rate growth fitting method both based on Lauritzen–Hoffman theory. It is proved that Lauritzen–Hoffman theory is of great significance for guiding the kinetic behavior of PCLTMC crystallization. [ABSTRACT FROM AUTHOR]