Photocurable polymers have become increasingly important for their quick prototyping and high accuracy when used in three dimensional (3D) printing. However, some of the common photocurable polymers are known to be brittle, cytotoxic and present low impact resistance, all of which limit their applications in medicine. In this study, thermal treatment was studied for its effect and potential applications on the mechanical properties, degradability and biocompatibility of glycerol-based photocurable polymers, poly(glycerol sebacate) acrylate (PGSA). In addition to the slight increase in elongation at break, a two-fold increase in both Young's modulus and ultimate tensile strength were also observed after thermal treatment for the production of thermally treated PGSA (tPGSA). Moreover, the degradation rate of tPGSA significantly decreased due to the increase in crosslinking density in thermal treatment. The significant increase in cell viability and metabolic activity on both flat films and 3D-printed scaffolds via digital light processing-additive manufacturing (DLP-AM) demonstrated high in vitro biocompatibility of tPGSA. The histological studies and immune staining indicated that tPGSA elicited minimum immune responses. In addition, while many scaffolds suffer from instability through sterilization processes, it was proven that once glycerol-based polymers have been treated thermally, the influence of autoclaving the scaffolds were minimized. Therefore, thermal treatment is considered an effective method for the overall enhancement and stabilization of photocurable glycerol-based polymeric scaffolds in medicine-related applications.