Degradable copolymers were synthesized by bulk copolymerization of 2,2-dimethyl trimethylene carbonate (DMCA) and ε-caprolactone (CL) using samarium (III) acetate as an initiator at 120 ºC for 24 h. The copolymers were characterized by Fourier transform infrared spectroscopy (FT-IR spectroscopy), proton nuclear magnetic Resonance Spectroscopy (¹H-NMR spectroscopy), size exclusion chromatography (SEC) and differential scanning calorimetry (DSC). The effect of the molar ratio in the DMCA to CL feed on the properties of the copolymers obtained was studied. The composition of the copolymers (F_CL/F_DMCA) matched the feed dosage. Conversion studies were performed and reactivity ratios of both monomers (r_n) were obtained; their values were r_CL = 5.54 for CL and r_DMCA = 2.28 for DMCA, which indicated that CL was more active than DMCA.