Al/Zn-cross-linked montmorillonite(Al/Zn-Mont) catalyst was prepared by montmorillonite(Na-mont),furthermore it was acidified by w(H2SO4) =15 % to get H+-Al/Zn-Mont.And the catalysts were studied by XRD,BET and NH3-TPD.The surface area of H+-Al/Zn-Mont increased from 29m2.g-1 to 225.8m2.g-1.Its interlamellar spacing increased from 1.25 nm to 1.45 nm.Different acetals and ketals were synthesized from glycol(1,2-propanediol),cyclohexanone(butanone,benzaldehyde)and catalyst which is Mont,Al/Zn-Mont and H+-Al/Zn-Mont,respectively.The results showed that H+-Al/Zn-Mont was an efficient catalyst for the synthesis of acetals(ketals),the yield of acetals(ketals) can reach above 95%.