Cobalt oxide (Co3O4) is a promising non-noble metal electrocatalyst for oxygen evolution reaction (OER), but it is hard to provide competitive performance relative to noble metal catalysts. In this paper, Cobalt oxide (Co3O4) nanowires/Ni foam (NF) for oxygen evolution reaction (OER) activity is enhanced by coupling NiCo-layered double hydroxide (NiCo-LDH) nanosheets on the surface. The prepared heterogeneous structure affects the electronic structure of Cobalt oxide (Co3O4), improving the intrinsic activity and resulting in an enhanced oxygen evolution reaction (OER) performance. The overpotential is only required 143 mV to reach 20 mA·cm−2 in an alkaline environment (1-M KOH). This paper provides a potential strategy for high-efficiency oxygen evolution reaction (OER).