| Summary: | In this work, a series of urchin-like Ce(HCOO)<sub>3</sub> nanoclusters were synthesized via a facile and scalable microwave-assisted method by varying the irradiation time, and the structure–property relationship was investigated. The optimization of the reaction time was performed based on structural characterizations and electrochemical performances, and the Ce(HCOO)<sub>3</sub>-210 s sample shows a specific capacitance as high as 132 F g<sup>−1</sup> at a current density of 1 A g<sup>−1</sup>. This is due to the optimal mesoporous hierarchical structure and crystallinity that are beneficial to its conductivity, offering abundant Ce<sup>3+</sup>/Ce<sup>4+</sup> active sites and facilitating the transportation of electrolyte ions. Moreover, an asymmetric supercapacitor based on Ce(HCOO)<sub>3</sub>//AC was fabricated, which delivers a maximum energy density of 14.78 Wh kg<sup>−1</sup> and a considerably high power density of 15,168 W kg<sup>−1</sup>. After 10,000 continuous charge–discharge cycles at 3 A g<sup>−1</sup>, the ASC device retains 81.3% of its initial specific capacitance. The excellent comprehensive electrochemical performance of this urchin-like Ce(HCOO)<sub>3</sub> offers significant promise for practical supercapacitor applications.
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