Poly(1,3-propanediol palmitate)/L-polylactic acid (PO3G-PA/PLLA) composite films were prepared by solution casting. The two raw materials used to prepare the film are 100% renewable. The experimental results of the composite films show that the addition of PO3G–PA can significantly improve the toughness and crystallinity of PLLA while keeping the thermal stability of the film unchanged. When PO3G–PA was added to the film at concentrations of 0%, 5%, 10%, 15%, 20%, and 25%, the elongation at break of the film reached 37.5%, 68.8%, 118.9%, 226.8%, and 95.9%, respectively. The crystallinity of PLLA could reach 4.5%, 6.19%, 10.59%, 23.00%, 25.28%, and 16.62%, separately. The accelerated degradation experiments at 60 °C showed that adding different quantities of PO3G-PA under neutral conditions had a minimal effect on the rate of PLLA film degradation. The degradation rate of the PLLA membrane can be successfully modified by varying the concentration of PO3G–PA under acidic and alkaline conditions.