<p>Supercapacitors hold significant promise for applications in portable electronics, electric transportation, and sustainable energy systems. Among various components, the electrode material plays a pivotal role in determining the overall performance of supercapacitors. Metal–organic frameworks (MOFs) are characterized by high porosity, low density, large specific surface area, uniform pore structure, and tunable pore size. These structural features render MOFs highly suitable as templates for fabricating hollow architectures, enabling diverse applications across multiple disciplines. Layered double hydroxides (LDHs), a class of cationic hydrotalcite-like materials, possess a lamellar architecture composed of positively charged metal hydroxide sheets and interlayer anions. Recently, LDHs have attracted extensive interest for use in supercapacitors owing to their unique layered configuration, high tunability, and impressive specific capacitance. In this study, Co-based MOF is employed as a structural template to synthesize CoNi-LDH with a well-defined hollow morphology. The synthesized CoNi-LDH achieves a peak specific capacitance of 1104 F g⁻¹ under a current density of 1 A g⁻¹. An asymmetric supercapacitor, constructed with CoNi-LDH as the cathode and activated carbon (AC) as the anode, delivers an energy density of 43.4 Wh kg⁻¹ at a power density of 750 W kg⁻¹. After 10,000 consecutive charge–discharge cycles at 5 A g⁻¹, the device maintains 80.6% of its initial capacitance. The templating strategy introduced herein mitigates the stacking issue commonly seen in LDH materials, enhances their electrochemical properties, and presents considerable potential for further investigation.</p>