Polyethylene-based separators are generally unsuitable for aqueous supercapacitors due to their poor wettability with the electrolyte, which impedes ion transport. However, incorporating Triton X-100 (2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol) into the aqueous sulfuric acid (H2SO4) electrolyte improves the wettability of polyethylene and facilitates ionic movement through its pores. In this study, Triton X-100 was added to 1.0 M H2SO4 at various concentrations (0.122%–1.210% V/V) to evaluate its impact on supercapacitor performance. Supercapacitors were assembled using activated carbon-filled carbon cloth electrodes, each of the above electrolytes and polyethylene sheet separators. Scanning electron microscopy revealed that the carbon cloth exhibited a uniform fiber distribution and high surface area for activated carbon integration. The polyethylene separator displayed a porous structure with an average pore size of 165 ± 35 nm. Triton X-100 significantly reduced the water contact angle from 101.5° (without surfactant) to 30.2° (with 1.21% V/V Triton X-100), enhancing polyethylene’s wettability. This change from hydrophobic to hydrophilic characteristics enabled the formation of an electrical double layer at the separator/electrolyte interface, improving ionic transport. However, higher Triton X-100 concentrations increased the electrolyte's viscosity, which impeded ion movement. The highest specific capacitance of 55.3 F/g (at a scan rate of 0.005 V s−1) was achieved with 0.488% V/V Triton X-100. The specific capacitance varied with surfactant concentration in a complex manner, influenced by micelle formation and precipitation. These findings were corroborated by cyclic voltammetry and AC impedance spectroscopy.