An environmentally benign method to accelerate the pinacol rearrangement in high temperature liquid water by the addition of CO2 was proposed.The effects of CO2 initial pressure and temperature on the kinetics of pinacol rearrangement were studied.The experimental results showed that the reaction rate could be greatly increased with the addition of CO2.The activation energies evaluated were 81.1 kJ·mol-1 without CO2,and 87.1 kJ·mol-1 with CO2 initial pressure at 0.2 MPa,which showed no significant difference.The main by-product was confirmed to be 2,3-dimethyl-3-butadiene by GC/MS and the possible reaction mechanism was proposed.