Hybrid materials have attracted tremendous attention because of their potential for achieving satisfactory lithium storage properties, which are promising to meet the growing demand of the powering market and consumer. In this study, we designed an effective strategy to synthesize a Co₃V₂O₈@NiCo LDH composite with a 3D hierarchical structure based on the assistant of PVP. With PVP-modified Co₃V₂O₈ as templates, NiCo LDH grew on the surface of Co₃V₂O₈ successfully and uniformly. As anode materials for LIBs, the obtained composite Co₃V₂O₈@NiCo LDH delivered remarkable capacity properties (1329.4 mA h g⁻¹ at 1 A g⁻¹ after 500 cycles), cycle stability and rate ability (893.1 mA h g⁻¹ at a high current density of 5 A g⁻¹ after 950 cycles). The outstanding lithium storage properties might be attributed to the complex three-dimensional structure, the combination of different components and the synergistic effect of hybrid materials.