The influence of zirconia polymorphs on methanol adsorption was investigated by FTIR technique. One terminal and two types of bridged methoxyl were formed on the am-ZrO2 and t-ZrO2 samples, while another tribridged methoxyl species was detected on the m-ZrO2 sample. During the formation of methoxyl, bridged hydroxyl species on the am-ZrO2 and m-ZrO2 was more active, while the terminal one on the t-ZrO2 sample was more active. The methoxyl was oxygenated by surface oxygen ions to be formate and further to be carbonate on the m-ZrO2 and am-ZrO2 samples. But for t-ZrO2, methoxyl could be directly oxygenated to be carbonate at RT, which implied that the surface oxygen ions on t-ZrO2 were more active than those on the two other samples.