Activated carbon (AC) modification has been intensively studied in order to design carbon electrodes with enhanced electrochemical performance. Hexadecyltrimethylammonium bromide (HDTMA) and Tween 80 were employed for enhancing the surface activity of AC via synergism. The synergistic effects of the mixed surfactants on AC surface activity in the light of interface behaviors were studied. Both field emission scanning electron micrographs and FTIR spectra indicated a successful adsorption of loaded surfactants. AC gained a good wettability originated from the surfactants, especially in the binary mixture (T80-HDTMA). The zeta potential results unveiled the positive charge density enhancement in the mixed surfactants system. Isoelectric point and point of zero charge implicate heterogeneous distribution of charges and the extent of surfactants treatment. Tween 80 displayed a significant size control dependence on AC particles. Electrochemical characterization revealed a higher specific capacitance and a decaying resistance of specific capacitance in AC-T80-HDTMA than AC-HDTMA at high concentration. In 5 g L−1 of NaCl, AC-T80-HDTMA (0.01 : 0.01 mM) exhibits the specific capacitance of 209.79 F g−1, at 0.8 V whereas AC-HDTMA (0.01 mM) and AC exhibited 186.5 F g−1, 178.9 F g−1, respectively. Moreover, the stability testing reveals a strong attachment of HDTMA in AC-T80-HDTMA than AC-HDTMA with the loss of 0.32% and 1.32%, respectively. The hypothetical synergistic mechanism of surfactants adsorption on the surface of AC was depicted as hydrophobic interaction and steric stabilization being the main keys for the synergy between cationic and nonionic surfactants. This study demonstrates the beneficial effects of mixed surfactants on AC electrode properties and discloses the impact on electrochemical performance.