In this work, three Cu metal-organic framework samples with tunable rhombic, squama, and trucated bipyramid morphologies have been synthesized at 0, 25, and 60 °C, respectively, and further employed as precursors to initially prepare Cu@C composites by the calcination-thermolysis procedure. Then Cu@C composites have been etched with HCl and subsequently activated with KOH to obtain activated porous carbon (APC-0, -25, and -60). Interestingly, APC-25 presents a loose multilevel morphology of cabbage and possesses the largest specific surface area (1880.4 m2 g-1) and pore volume (0.81 cm3 g-1) among these APC materials. Consequently, APC-25 also exhibits the highest specific capacitance of 196 F g-1 at 0.5 A g-1, and the corresponding symmetric supercapacitor cell (SSC) achieves a remarkable energy density of 11.8 Wh kg-1 at a power density of 350 W kg-1. Furthermore, APC-25 shows excellent cycling stability, and the loss of capacitance is only 7.7% even after 10000 cycles at 1 A g-1. Significantly, five light-emitting diodes can be lit by six SSCs, which proves that APC-25 can be used in energy storage devices.