In this work, a class of polyol solid-solid phase change material where Neopentyl glycol is mixed in 6 and 2 wt.% of Pentaerythritol and was synthesized by physical blending method to obtain homogeneous mixture and thermally cycled for 500 times. The surface morphology, chemical composition, crystal phase identification, thermal degradation, and phase change phenomena were characterized. The phase transition temperatures and enthalpies upon heating and cooling of 6 and 2 wt.% of Pentaerythritol are found to be 43.1 °C, 133 J g-1, and 28.2 °C, 119 J g-1, and 41.2 °C, 121 J g-1, and 28.5 °C, 106 J g-1, respectively which suits for electronic system to keep under operating zone. Laser Flash Apparatus was used to find the thermal diffusivity and thermal conductivity value was calculated. Further, the effect of heat transfer in binary polyol mixtures were experimentally analysed through conventional heat sink for electronic cooling application.