The nano-Co/Ce-V-Zr-TiO2 catalysts with the selective catalytic reduction (SCR) were prepared by methods of Sol-gel, impregnation (IM) and co-precipitation (CP). The phase compositions, microstructures and specific surface area of the catalysts were analyzed by BET, XRD and SEM, respectively. The effect of CeO2, CoO, V2O5 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 Co/Ce-V-Zr-TiO2 catalysts were made up of nanometer grains. Compared to conventional TiO2 catalysts, the as-prepared Co/Ce-V-Zr-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 8 wt%Co/Ce-V-Zr-TiO2 catalysts reached 98.3% at the reaction temperature of 550 oC. Furthermore, the activity of Co/Ce-V-Zr-TiO2 catalysts were improved by the Co loading, however, further increasing the Co loading lead to decrease the catalysis activity.