In this study, diphenyl sulfide (Ph2S) was employed to prepare a series of Ph2S-modified Pd/C catalysts (Pd-Ph2S/C). Catalyst characterization carried out by Brunner-Emmet-Teller (BET), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and CO chemisorption uptake measurements suggested a chemical interaction between Ph2S and Pd. The ligand was preferably absorbed on the active site of Pd metal but after increasing the amount of Ph2S, the adsorption of Ph2S on Pd metal tended to be saturated and the excess of Ph2S partially adsorbed on the activated carbon. A part of Pd atoms without adsorbing any Ph2S still existed, even for the saturated Pd-Ph2S/C catalyst. The Pd-Ph2S/C catalysts exhibited a good selectivity of p-chloroaniline (p-CAN) in the hydrogenation of p-chloronitrobenzene (p-CNB). However, the chemisorption between Ph2S and Pd was not so strong that part of Ph2S was leached from Pd-Ph2S/C catalyst during the hydrogenation, which caused the decline of the selectivity of p-CAN over the used Pd-Ph2S/C catalyst. Resulfidation of the used Pd-Ph2S/C catalyst was effective to resume its stability, and the regenerated Pd-Ph2S/C catalyst could be reused for at least ten runs with a stable catalytic performance. (C) 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.