The reductive alkylation of p-nitroaniline with 5-methyl-2-hexanone over copper-based catalysts was investigated. Furthermore, the catalysts were characterized using the techniques of XRD, H-2-N2O titration, H-2-TPR, NH3-TPD and pyridine-FTIR. The results showed that the addition of Mn, Ba and La into Cu-SiO2 catalyst played an important role in the improvement of the selectivity towards N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (BMPPD). The highest selectivity towards BMPPD over 58CuO-9MnO(2)-BaO-1La(2)O(3)-30SiO(2) (wt.%) catalyst could be ascribed to the best dispersion of copper (i.e., the highest hydrogenation ability) and the most amounts of the surface Lewis acidic sites.