Due to the difficult access of the electrolyte into the nanoconfined space of nanoporous reduced graphene oxide (rGO) electrodes, achieving the optimal electrochemical performance of these devices becomes a challenge. In this work, the dynamics of interfacial-governed phenomena are investigated during a voltage-controlled electrochemical activation of nanoporous rGO electrodes that leads to an enhanced electrochemical performance in terms of areal capacitance and electrochemical impedance.