Herein, the regularly hierarchical W18O49-MoS₂ nanospheres comprising the urchin-like W18O49 nanospheres and MoS₂ nanosheets are facile constructed. The MoS₂ nanosheets wrapped around the nanochains of W18O49 nanospheres not only provide synergistic effect, but also enhance the structural stability. As expected, the hybrid hierarchical materials exhibit superior electrochemical performance.