The reaction of di(1-naphthyl)methane (DNM) was investigated as a model reaction for coal liquefaction using Fe, Ni, and Pd/C both in the presence and in the absence of sulfur. The results show that Fe, Ni, and Pd/C mainly catalyzed DNM hydrogenation, whereas added sulfur, which was likely to react with Fe, Ni, and Pd/C to form their sulfides, retarded DNM hydrogenation but promoted DNM hydrocracking. According to the results, we consider that the metals predominately catalyzed biatomic hydrogen transfer, whereas their sulfides selectively promoted monatomic hydrogen transfer.