The self-catalytic role of zirconium n-propoxide has been investigated with respect to the synthetic parameters of ZrO2/Y2O3-CeO2 compound powders. When zirconium n-propoxide is prehydrolyzed, the gelation time is prolonged, resulting in a more transparent gel. It is found that gelation time can be shortened with a high concentration of tetraethoxysilane in the presence of a small amount of zirconium n-propoxide. On the basis of the synthetic data, a mechanism for the zirconium n-propoxide catalytic reactions has been discussed. A linear correlation between the mixing level and metal content holds up to 45 mol% of ZrO2/Y2O3 under the studied conditions.