Mesoporous cobalt doped nickel vanadate hierarchical microspheres were developed via microwave-assisted approach. Interestingly, the introduce of cobalt renders smooth microspheres transforming into hierarchical microspheres with uniform size self-assembled from nanorods, which displays enhanced specific surface area. Benefitting from the unique morphology and synergistic effect of cobalt and nickel, cobalt doped nickel vanadate hierarchical microspheres exhibit significantly improved performance with a higher rate capability (73.7% at 20 times) and a higher capacitance retention (82.2% after 10000 charges and discharges) compared with pure nickel vanadate. This novel design strategy has great potential for promoting the practical use of electrochemical energy storage devices.