Polyesters based on polyols have emerged as promising biomaterials for various biomedical applications, such as tissue engineering, drug delivery systems, and regenerative medicine, due to their biocompatibility, biodegradability, and versatile physicochemical properties. This review article provides an overview of the synthesis methods, performance, and biodegradation mechanisms of polyol-based polyesters, highlighting their potential for use in a wide range of biomedical applications. The synthesis techniques, such as simple polycondensation and enzymatic polymerization, allow for the fine-tuning of polyester structure and molecular weight, thereby enabling the tailoring of material properties to specific application requirements. The physicochemical properties of polyol-based polyesters, such as hydrophilicity, crystallinity, and mechanical properties, can be altered by incorporating different polyols. The article highlights the influence of various factors, such as molecular weight, crosslinking density, and degradation medium, on the biodegradation behavior of these materials, and the importance of understanding these factors for controlling degradation rates. Future research directions include the development of novel polyesters with improved properties, optimization of degradation rates, and exploration of advanced processing techniques for fabricating scaffolds and drug delivery systems. Overall, polyol-based polyesters hold significant potential in the field of biomedical applications, paving the way for groundbreaking advancements and innovative solutions that could revolutionize patient care and treatment outcomes.