Abstract Metal selenides are essential electrode materials for promising electrochemical energy storage with comparable or improved electrochemical performance than metal oxides. Herein, Se/NiSe 2 /CoSe 2 (S/NS/CS) is fabricated using a solvothermal approach with the assistance of polyethyleneimine, followed by annealing at different temperatures (300, 400, 500, and 600 °C) for one hour under an argon atmosphere. After annealing, all electrodes’ physical and electrochemical properties were examined, which determined that the best electrode is NiCo 2 O 4 /NiO ( NCO/NO) formed at 500 °C. Additional hydrothermal method uses NCO/NO with SeO 2 as a selenium source to prepare S/NS/CS nanocomposite, with a specific surface architecture that enables easy ion movement and robust conductivity, giving it exceptional electrochemical energy storage properties. It exhibited a remarkable capacitance of 468 F g −1 at a current density of 0.5 A g −1 . For practical applications, the hybrid S/NS/CS//AC device was designed using S/NS/CS as a positive electrode and commercial activated carbon (AC) as a negative electrode. The asymmetric device demonstrated an excellent capacitance of 142 F g −1 (189 C g −1 ) and a superb specific energy of 44 Wh kg −1 at a specific power of 840 W kg −1 at a current density of 1 A g −1 , providing 80 % capacity retention and 100 % coulombic efficiency after 5000 cycles.