The heteropoly acids contained manganese, chromium, molybdenum, and vanadium were prepared, which was characterized by IR, XRD and ICP, and revealed that the compounds synthesized in the present work were Keggin structure.The catalytic performance of the heteropoly acids for the synthesis of benzaldehyde glycol acetal were investigated under the reaction condition of reaction temperature 120 °C, amount of catalyst 2.0%, reaction time 1 h, and the yield of benzaldehyde glycol acetal can obtain to 72.5%.