A series of nanocrystal zirconia samples were synthesized, characterized and studied for the esterification reaction. The results showed that the solvothermal method under different solvent/alkoxide molar ratios led to remarkable effect on the amount of carbon residue remained on the surface of catalysts resulting in the difference in proton species-support interaction behavior. Moreover, the esterification activity of W/ZrO2 varied distinctly with the solvothermal synthesis condition of nanocrystal zirconia.