Co3V2O8 hexagonal pyramid was successfully fabricated via a simple hydrothermal process and subsequent heat treatment. The inner structure of the hexagonal pyramid was further adjusted by controlling the size of Co7V4O16(OH)2(H2O) precursors. Hierarchical Co3V2O8 hexagonal pyramid with height of 1μm were orderly constructed from 60–80nm inter-connected particles, showing numerous interval voids. Benefiting from its unique structure, the as-prepared sample showed higher electrochemical performance as an anode material for lithium-ion batteries than that of another bulk sample with height of 5μm and adhesive inner structure. When tested at a current density of 500mAg−1, the hierarchical Co3V2O8 hexagonal pyramid exhibited good rate capacity, high cycling stability, and excellent discharge capacity up to 712mA h g−1, making it promising electrode materials for lithium-ion batteries.