Reactions of acetic acid were conducted with alkali (KOH) and zirconia (ZrO 2 ) catalysts in supercritical water (SCW) (673K and 25MPa-40MPa). For comparison, we also conducted the experiments without catalyst and/or water at the same reaction conditions. Decarboxylation of acetic acid with zirconia in supercritical water formed acetone, CO 2 , and water without forming any other compound. On the other hand, decomposition of acetic acid with alkali produced methane (CH 4 ) and CO 2 with acetone. Without water and/or catalyst, the main products were also CO 2 and CH 4 (without catalyst) or acetone (with ZrO 2 ); however, by-products, such as a water-insoluble compound were formed. The structure of zirconia was changed during reaction in supercritical water. The rate of decarboxylation of acetic acid exerted an effect on the particle size of zirconia.