The Ce-V/TiO2 catalysts with the selective catalytic reduction (SCR) were prepared by method of Sol-gel and insuccation. The phase compositions, microstructures and specific surface area of the catalysts were analyzed by XRD, SEM and BET, respectively. The effect of CeO2 and V2O5 loading and reaction temperature on the catalytic performances of the as-prepared catalysts was investigated by using the selective reduction of NOx with NH3. The results showed all the as-prepared Ce-V/TiO2 catalysts were made up of nanometer grains. Compared to conventional TiO2 catalysts, the as-prepared Ce-V/TiO2 catalysts possessed better catalytic performance, higher adsorbability and larger area of contact with reactant, which is due to large quantity surface micropores. The NOx conversion of SCR over 5wt%Ce-10wt%V/TiO2 catalysts reached 96.2% at the reaction temperature of 500 oC.