Abstract The pursuit of electrode materials with porous structure is one of effective strategies to improve the electrochemical performance of energy storage devices. Herein, we report a facile trisodium citrate-assisted microwave method to prepare CeO2 mesoporous microspheres constructed from nanoparticles. The composite, structure and morphology of the resultant are characterized by several techniques. Benefiting from the unique integrated structure, the as-prepared CeO2 electrode exhibits a high specific capacitance of 415 F g−1 after 3000 cycles at 0.1 mA cm−2 in supercapacitor, a good lithium storage capacity of 529 mAh g−1 after 100 cycles at 0.5 mA cm−2 and a distinguished rate capability.