Biodegradable and bioabsorbable polymers have drawn considerable attention because of their mechanical properties that mimic human soft tissue. Poly(l-lactide-co-ε-caprolactone) (PLCL), the copolymer of L-lactic (LA) and ε-caprolactone (CL), has been applied in many tissue engineering and regenerative medicine fields. However, both the synthesis of PLCL and the structure-activity relationship of the copolymer need to be further investigated to allow tuning of different mechanical properties. The synthesis conditions of PLCL were optimized to increase the yield and improve the copolymer properties. The synthetic process was evaluated by while varying the molar ratio of the monomers and polymerization time. The mechanical properties of the copolymer were investigated from the macroscopic and microscopic perspectives. Changes in the polymerization time and feed ratio resulted in the difference in the LA and CL content, which, in turn, caused the PLCL to exhibit different properties. The PLCL obtained with a feed ratio of 1:1 (LA:CL) and a polymerization time of 30 h has the best toughness and elasticity. The developed PLCL may have applications in dynamic mechanical environment, such as vascular tissue engineering.