A series of quaternary ammonium zirconium salt co doped phosphotungstic acid catalysts were prepared by ion exchange method. The structure, stability and acidity of the composite catalysts were characterized by SEM, FT-IR, XRD, XPS, TGA-DTG, and n-butylamine potential method. And its catalytic performance during acetalization of benzaldehyde (BH) and glycol (GL) were assessed. Meanwhile, the effects of catalyst amount, the molar ratio of alcohol to aldehyde, the amount of water carrying agent and the reaction time on the yield of benzaldehyde glycol acetal (BEGA) were examined. The results showed that the TB_0.5Zr_0.5H_0.5PW (TB was tetrabutylammonium bromide) catalyst had excellent catalytic activity. The strong Bronsted acidity, synergistic effect between Bronsted and Lewis acid centers, and "pseudo liquid phase" characteristics were the reasons for the high activity of the catalyst. Using TB_0.5Zr_0.5H_0.5PW as the catalyst, the yield of BEGA can reach 94.6% under the conditions optimized via response surface methodology (RSM) with BH/GL molar ratio of 1.5:1, catalyst amount of 1.9% of BH, reaction time of 3 h, and amount of cyclohexane 12.6 mL. The TB_0.5Zr_0.5H_0.5PW solid acid catalyst still exhibited excellent catalytic performance after 6 further uses, indicating that the catalyst had promising industrial application possibilities.