Polyols, a typical type of alcohol containing multiple hydroxyl groups, are being regarded as a new generation of a green energy platform. In this paper, the decomposition mechanisms for three polyol molecules, i.e., 1,2-propanediol, 1,3-propanediol, and glycerol, have been investigated by quantum chemistry calculations. The potential energy surfaces of propanediols and glycerol have been built by the QCISD(T) and CBS-QB3 methods, respectively. For the three molecules studied, the H2O-elimination and C-C bond dissociation reactions show great importance among all of the unimolecular decomposition channels. Rate constant calculations further demonstrate that the H2O-elimination reactions are predominant at low temperature and pressure, whereas the direct C-C bond dissociation reactions prevail at high temperature and pressure. The temperature and pressure dependence of calculated rate constants was demonstrated by the fitted Arrhenius equations. This work aims to better understand the thermal decomposition process of polyols and provide useful thermochemical and kinetic data for kinetic modeling of polyols-derived fuel combustion.