One of the significant challenges of vanadium redox flow batteries is connected to the negative electrode where the main reaction of V(II)/V(III) and the side reaction of hydrogen evolution compete. To address this issue, we used titanium carbide (Ti3C2Tx) MXene coating via drop-casting to introduce oxygen functional groups and metals on the carbon electrode surface. Characterization through scanning electron microscopy and X-ray photoelectron spectroscopy confirmed the even distribution of Ti3C2Tx MXene on the electrodes and the presence of titanium and termination groups (–O, –Cl, and –F). The cyclic voltammetry analysis of MXene-coated electrodes showed more sharp electrochemical peaks for the V(II)/V(III) reaction than thermal-treated electrodes, even at relatively high scan rates. Notably, a relatively high reaction rate of 5.61 × 10−4 cm s−1 was achieved for the V(II)/V(III) reaction on MXene-coated electrodes, which shows the competitiveness of the method compared to thermal treatment (4.17 × 10−4 cm s−1). The flow battery tests, at a current density of 130 mA cm−2, using MXene-coated electrodes showed pretty stable discharge capacity for over 100 cycles. In addition, the voltage and energy efficiency were significantly higher than those of the system using untreated electrodes. Overall, this work highlights the potential application of MXene coating in carbon electrode treatment for vanadium redox flow batteries due to remarkable electrocatalytic activity and battery performance, providing a competitive method for thermal treatment.