Here, we report the development of high-performance supercapacitor devices using manganese-doped zinc oxide nanowires (Mn-doped ZnO NWs) and copper-doped zinc oxide nanoparticles (Cu-doped ZnO NPs) as a positive electrode with MXene as a negative electrode. Both transition metal (TM)-based electrodes were used separately with MXene, and the performance was tested. When used in combination with MXene as a second electrode, TM-ZnO samples displayed a major increase in the supercapacitors’ performance. The highest-performance supercapacitor recorded values of 151 F/g specific capacitance along with 84 Wh/kg energy density and a power density of 75 kW/kg. Electron paramagnetic resonance and photoluminescence spectroscopy of Mn/Cu-doped ZnO reveals intrinsic and extrinsic defect signals, which were discussed and attributed to the enhancement of the capacitive performance …