The Cu/Al2O3, Cu/MgAlO, Cu/MgO and Cu-Ni/MgAlO catalysts (60 wt%) were studied for the selective hydrogenation of biphenyl (BP) to cyclohexylbenzene (CHB). The results showed the relatively high dispersion but low reducibility of Cu in the Cu/Al2O3. The acidic surface of Al2O3 caused the electron-deficient Cu that enhanced the adsorption of aromatic rings and thus led to the higher intrinsic activity for the hydrogenation of aromatic rings over the Cu/Al2O3, while the basic surface of MgO played the just opposite roles. The Cu/MgAlO possessed the suitable surface acidity and basicity and thus the high density of surface Cu active sites. Thus, it exhibited the higher overall activity than the Cu/Al2O3 and Cu/MgO for the hydrogenation of BP. However, the heats for the adsorption of toluene and H2 were significantly lower on Cu than those on Ni, which accounted for that the Ni was much more active than Cu for the hydrogenation of BP and CHB. Further studies showed that the activation energies for the hydrogenation of BP and CHB on Cu were high and differ greatly, resulting in the high conversion of BP with high selectivity to CHB over the Cu catalysts. On the other hand, the activation energies were significantly lower and did not differ so much on Ni, leading to the high conversion of BP and CHB for the formation of bicyclohexyl. Finally, the addition of a small amount of Ni (1 wt%) into the Cu/MgAlO greatly increased the conversion of BP under relative lower temperature while maintained the high selectivity to CHB.