Synthetic polyesters have become an integral part of various biomedical and engineering fields, such as tissue scaffolding and therapeutic delivery. While polymer and copolymers derived from lactide, glycolide, ε-caprolactone, and p-dioxanone still dominate the biomedical industry, many new polymerization strategies and materials are being explored, including thermal polycondensation. Adjusting curing conditions and monomer feed ratios allows for easy control over the macromolecular properties of polymers resulting from thermal polyesterification. In terms of mechanical versatility, crystallinity, hydrophobicity, and biocompatibility, polyesters synthesized thermally have displayed a wide range of properties. These properties allow for materials to be tailored according to the needs of a particular application. Additionally, several natural metabolites—some endogenous to human biochemical pathways—are able to serve as precursors for a significant number of these polyester thermosets. While many starting materials have been reused and reformulated to produce novel polyesters, new small molecules are continually being introduced to the materials community as promising monomer candidates to continue the growth of this research area. To date, polyesters synthesized with thermal polycondensation have already produced a tremendous amount of in vitro and in vivo success.