The reaction rules of selective hydrogenation p-chloronitrobenzene(p-CNB) to p-chloroaniline(p-CAN) over skeletal copper（S-Cu） catalyst were studied. The microstructure of S-Cu was characterized by XRD, BET and SEM. The effects of solvent, reaction temperature, reaction pressure and concentration of substrate on the conversion of the reaction and the selectivity of target product have been investigated. Under the optimized reaction conditions of n(p-CNB) = 7 mmol, m(S-Cu) = 0.5 g (wet weight), V(CH3OH) = 20 mL, 60 ℃, and P（H2）= 1.0 MPa, the conversion of p-CNB was up to 100% and the selectivity of p-CAN was 97.9% in 120 minutes.