Developing state-of-the-art non-noble metal catalysts for the oxygen evolution reaction holds a key to the production of electrolytic hydrogen. Herein, self-supported hierarchical NiFe LDH/VO(OH)2 nanoflowers/nanosheets grown on a Ni foam have been synthesized via a two-step hydrothermal method. Numerous fine VO(OH)2 nanosheets grown on NiFe LDH nanoflowers enlarge the contact area for the electrolyte penetration and facilitate ion diffusion, while the three-dimensional structure of the material also provides an extensive active surface area and plentiful accessible active sites. Moreover, the strong synergistic interaction between VO(OH)2 and NiFe LDHs subtly modulates the electronic environment, accelerating the electron/charge transfer. As a result, the catalyst exhibits excellent electrochemical performance for OER giving a voltage of 1.51 V to achieve the current density of 100 mA cm-2 and possessed a Tafel slope of 65 mV dec-1 in 1.0 M KOH. In addition, the material exhibited remarkable long-term durability and stability during the 40 h measurement. This investigation provides a promising strategy for rationally designing high-efficiency metal electrocatalysts with hierarchical multi-dimensional nanostructures for OER.