Synthetic polymers, especially aliphatic polyesters gain success in biomedical applications due to better biodegradation profile owing to susceptible ester linkage in their backbone and controllable network and functionality. Poly(glycolic Acid) (PGA) is the simplest aliphatic polyester and considered as best profiled polymer for biodegradation and biocompatibility. Commercialized product of PGA synthesized by ring opening polymerization of glycolide (a cyclic diester). Whereas, it can also be synthesized by direct polycondensation of glycolic acid (GA), however, it is not well explored yet, due to poor thermal stability and difficulty in synthesis of high molecular weight PGA. In present research, high molecular weight and highly crystalline PGA was successfully synthesized by direct polycondensation of glycolic acid (GA) via combination of melt/solid and solid state polycondensation (SSP) with thermally induced crystallization. The obtained polymers were analyzed in terms of molecular weight and thermal properties.