CuSO ₄/SiO ₂ solid acid catalysts were prepared using sol-gel technique and impregnation method, and then characterized by XRD, low temperature N ₂-adsorption and NH ₃-TPD. The effects of calcination temperature of catalysts, CuSO ₄ loading, the molar ratio of benzaldehyde to glycerol, reaction time and amount of deaquation reagent on the synthesis yield were discussed. The results show that CuSO ₄ is highly dispersed over surface of SiO ₂ to form mesoporous solid acid catalysts with medium acid strength and high specific surface. CuSO ₄/SiO ₂ showed good catalytic activities and stabilities in the condensation of benzaldehyde with glycerol to produce benzaldehyde glycerol acetals. The optimum preparation conditions are as follows: CuSO ₄ loadings 15%, and calcination temperature 550 ℃. The optimum reaction conditions are as follows: molar ratio of benzaldehyde to glycerol is 1∶1.1, the weight percentage of catalyst in reaction mixture is 1%, and volume of cyclohexane is 10 mL and reaction time 2 h. Under the optimum reaction conditions, the yield of benzaldehyde glycerol acetal can reach 92.5%.