The specific heats (Csp) of neat polyvinyl alcohol (NPVOH) and 40 phr glycerol plasticized polyvinyl alcohol (PPVOH) were measured using a method known as power compensate differential scanning calorimetry. A high purity sapphire (Al2O3) was used as a reference material. NPVOH has a melting temperature of approximately 480 K, while PPVOH has a value of 30 K lower than NPVOH. The amplitude increment of Csp for NPVOH was also higher than PPVOH at melting stage. Overall, Csp of NPVOH is lower than PPVOH because glycerol has reduced the rigidity of PVOH and subsequently induced the motion of molecular structure at an elevated temperature. Based on the specific heat outcomes, neat PVOH and glycerol plasticized PVOH required 1173.544 J/g and 1946.631 J/g, respectively, to heat from 330 to 550 K.