In this work, we have optimized and fabricated pristine molybdenum dioxide (MoO2) electrodes over the Silicon (Si) substrate and examined the impact of various ion-loaded aqueous electrolytes on their electrochemical behavior. The sputtered electrodes exhibited a high crystalline structure and a very low resistivity. These highly conductive electrodes were tested in three different aqueous electrolytes (acidic, neutral, and alkaline) to establish a relation between the electrode and the nature of the electrolyte to achieve optimal electrochemical performance and cyclability. The electrochemical kinetics showed that the charge storage mechanism was unique for all the electrolytes. The capacitive current was dominant in the neutral electrolyte, whereas it was diffusive dominant in alkaline and 70% capacitive in the acidic electrolyte. Our findings indicated that the MoO2@Si electrode exhibited superior electrochemical activity in an acidic electrolyte. The electrode showed a voltage window of 0.6 V with an areal capacity of 24 mF/cm2 at 0.1 V/s scan rate. Moreover, the electrode also demonstrated excellent cyclability and capacitance retention (∼145%) till 5000 cycles. These results highlighted that the binder-free MoO2@Si electrode showed outstanding electrochemical activity and stability, which makes it suitable for sulfuric acid electrolyte-based energy storage systems.