<p>Herein, we proposed a simple ultrasonic-assisted solution mixing method to prepare a series of CeO₂@Cu₂O composite electrode materials with varying content of Cu₂O (5%, 10%, 15%). Initially, CeO₂ nanospheres (NSs) and Cu₂O microspheres (MSs) were synthesized by the solvothermal process. The heterostructure composites and the counterparts’ features were meticulously inspected with structural and morphological techniques. Peak shifting in X-ray diffraction indicates the formation of interfacial contact, which is further corroborated by X-ray photoelectron spectroscopy analysis. Spherical features of CeO₂ and Cu₂O species were confirmed through field emission scanning electron microscopy and transmission electron microscopy studies. Optical studies using UV-Vis spectroscopy demonstrated a decrease in bandgap of CeO₂ NSs with increasing Cu₂O content, reflecting better electronic interaction and potential charge transfer at the interface. Among the composites,&#xa0;CeO₂@Cu₂O-10 has shown enhanced electrochemical performance. Notably, CeO₂@Cu₂O-10 delivered a specific capacitance of 527&#xa0;F g^− 1 at 0.5&#xa0;A g^− 1. Interestingly, CeO₂@Cu₂O-10 composite exhibits remarkable cyclic stability (97.4% after 5000 cycles). The obtained heterostructure provides more efficient storage performance than its counterparts. Further, a satisfactory practical performance is noticed from an asymmetric coin cell assembled with CeO₂@Cu₂O-10 as positive and commercial activated carbon as negative electrodes. A facilely synthesized CeO₂@Cu₂O composite with promising results suggests its possible application in the field of energy storage.</p>