Coffee, as one of the most traded resources, generates a vast amount of biogenic by-products. Coffee silver skins (CSS), a side stream from the roasting process, account for about 4 wt.%. Despite the abundancy of CSS, possible routes to generate added value for broad applications are limited. Herein, we present an approach to use CSS as a precursor material for supercapacitor electrodes. KOH activated carbon (AC) was produced from CSS. The resulting AC—CSS was characterized by X-ray diffraction, gas sorption analysis, scanning electron microscopy, and Raman spectroscopy. The highly porous AC—CSS exposes a specific surface area of more than 2500 m2 g−1. Electrodes formed with AC—CSS were electrochemically characterized by performing cyclic voltammetry and galvanostatic cycling. The electrodes were further assembled into a supercapacitor device and operated using 1 M sulfuric acid as electrolyte. In addition, various quinones were added to the electrolyte and their impact on the capacitance of AC—CSS electrodes was analyzed. In this work, we were able to show that CSS are a valuable source for supercapacitor applications and that coffee-waste-derived quinones can act as capacitance enhancers. Thus, the findings of this research show a valuable path towards sustainable and green energy storage solutions.