Polyols are multifunctional alcohols, with branched structures, where each arm terminates with an –OH group. These free –OH groups have been utilised to make a variety of polymer structures ranging from cross-linked to linear to starshaped. This review presents a comprehensive account of polyol-based polymers in biomedical applications. The advantages afforded by polyolbased biodegradable polymers are detailed in this review, alongside a general historical perspective on the development of biodegradable polymers. The major advantage of these polyols is that they are endogenous to the human body. Synthesis strategies and fabrication techniques to mould these materials into three-dimensional (3D) scaffolds are discussed. Modifications to the conventionally used polyol-based polyesters have been achieved by chemically incorporating drugs/ bioactives or by preparing nanocomposites. This review discusses the physicochemical properties and biological responses of these polymers relevant in biomedical applications and further outlines the need for improving their processability and performance. © 2018, © 2018 Institute of Materials, Minerals and Mining and ASM International Published by Taylor & Francis on behalf of the Institute and ASM International.