The copper cobaltite chalcogenides were designed and developed via a simple and economically effective electrochemical route followed by the hydrothermal anion-exchange process without altering the morphological features. The systematic synthetic approach provided spinel crystalline-structured copper cobalt sulfide (CuCo 2 S 4 ) through in situ co-deposition and copper sulfide/cobalt sulfide composite (CuS/CoS) via layer-by-layer deposition. Obtained high-resolution scanning electron microscopy explains the unique dendrite morphology of copper cobalt sulfide (CuCo 2 S 4 ) with a primary midrib followed by secondary and tertiary trunks, whereas CuS/CoS governs a distinct CuS dendrite covered with thin CoS sheets homogeneously. Furthermore, the CuCo 2 S 4 electrode material governed a superior charge storage property in supercapacitor application with a capacitive value of 966−676.8 C g −1 at a current density ranging from 10 to 40 A g −1 with a 70.15% retention value, whereas CuS/ CoS delivered only 455.3−278.8 C g −1 at current densities with 61.23% retention. The promising faradaic behavior of the asprepared material was attributed by the stable charge-discharge profile at different applied current densities as 10, 20, 30, 40, and 10 A g −1 for 5000 cycles for CuCo 2 S 4 and CuS/CoS electrodes, respectively. To evaluate real-time charge storage behavior, an asymmetric device was assembled by coupling the CuCo 2 S 4 electrode with activated carbon electrode using a 3 M KOH aqueous electrolyte. The fabricated device delivered 126.8 and 81.45 C g −1 at 10 and 50 A g −1 , respectively. Moreover, the device demonstrated excellent cycling stability up to 5000 cycles at 50 A g −1 with 96.70% capacitive retention. Thus, the present work demonstrates the most effective strategy to exploit the synergistic effect of bimetal ions to boost the charge storage properties of a ternary chalcogenide electrode.