The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni3S2, Fe5Ni4S8, and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe5Ni4S8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.