High OER activity electrocatalysis of NiFeOx/Bi2WO6 was synthesized by a simple chemical coupling method. The studies of SEM, TEM, XRD, XRF and XPS certified the strong coupling between NiFeOx nanosheets and Bi2WO6 nanosheets. Significantly, the electrochemical test results revealed that the NiFeOx/Bi2WO6 with good activity and stability for OER under alkaline conditions. The increased performance was attributed to the synergistic effect of the NiFeOx Ns which grown uniformly on the Bi2WO6 Ns, the abundant Bi-O-Fe, W-O-Fe, W-O-Ni and Bi-O-Ni species act as strong bonds between NiFeOx Ns and Bi2WO6 Ns and the Fe-ion and oxygen vacancies presence in NiFeOx Ns, which can significantly increase the ECSA and active sites, enhanced the electron transfer capacity, decreased charge-transfer resistance, stabilizes Ni2+ and improved conductivity in the process of electrochemistry. As results, the synergistic effect of NiFeOx Ns, oxygen vacancies and tight-coupled endowed impressive performance of NiFeOx/Bi2WO6 for OER.