Poly(glycolic acid) (PGA) is an essential biopolymer due to its thermal and mechanical properties and biodegradability which provide utility for medical applications and renewable industry. For biomedical applications, production of PGA with high molecular weight is an essential factor to possess adequate mechanical stability. Primary pathways for PGA synthesis are ring-opening polymerization of glycolide (ROP), direct polycondensation of glycolic acid, and solid-state polycondensation of halogen acetates. For PGA synthesis, different systems have been developed with using varying parameters including catalysis, initiators, solvents, and reaction temperature. This review summarizes the different synthesis pathways and physicochemical properties of PGA. Biomedical applications of PGA are also discussed.