Advances in electrochemical interfaces have greatly facilitated the development of new energy systems that can replace traditional fossil fuels. Oxygen evolution reaction (OER) is the core reaction in the new energy conversion system to produce hydrogen. Here, nanorods structure of Mn3O4/Co9S8–Ni3S2/NF-4 was designed and assembled. The Mn3O4 has served as an appropriate matrix to build a composite structure with Co9S8–Ni3S2 to enhance the stability of catalyst. And the introduction of Mn regulated the electronic structure of Ni and Co, which increased the OER activity of matericals. Further characterization and electrochemical testing have suggested that between polymetallic can effectively optimize conductivity and enhance reaction kinetics. Mn3O4/Co9S8–Ni3S2/NF-4 can achieve overpotential of 188 mV at the current density of 10 mA cm−2 in alkaline solution, with small Tafel slope of 43.2 mV dec−1 and satisfactory stability of 30 h at 10 mA cm−2. This work may show a feasible reference in the design of high-efficient OER catalysts.