The effect of Fe, Co and Ni promoters on supported MoS₂ catalysts for hydrogenation of nitroarenes were systematically investigated via experiment, characterization and DFT calculation. It was found that the addition of promoters remarkably improved the reaction activity in a sequence of Ni > Co > Fe > Mo. Meanwhile Ni promoted catalyst with the best performance showed good recyclability and chemoselectivity for a wide substrate scope. The characterization results revealed that the addition of promoters decreased the interaction between Mo and support and facilitated the reductive sulfidation of Mo species to produce more coordinated unsaturated sites (CUS). DFT calculations showed that the addition of promoters increased the formation of CUS, and enhanced the adsorption of hydrogen. The influence degree of promoters followed the sequence Ni > Co > Fe > Mo, which was consistent with those of the activities. Nitrobenzene hydrogenation and hydrogen activation occurred at the S and Mo edge, respectively. The adsorbed hydrogen diffused from the Mo edge to the S edge to participate in the hydrogenation reaction. Mechanism investigation showed that the main reason for increased activity by the addition of promoters was the increase of amounts of CUS and the secondary reason was the augmentation of intrinsic activity of CUS. The present studies give a new understanding for promoter modified MoS₂ catalysts applied for hydrogenation of nitroarenes.