SO4 2- /TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions were also found, that is, the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450℃, and the soaked consistency of H2SO4 is 0.5mol·L-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as catalyst and revealed high catalytic activity. Under the condition that the molar ratio of aldehyde/ketone to glycol was 1:1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused. SO4 2- / TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions were also found, that is the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450 ° C, and the soaked consistency of H2SO4 is 0.5 mol·L-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as the catalyst and revealed high catalytic activity. Under the conditions that the molar ratio of aldehyde / ketone to glycol was 1: 1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused.