This work demonstrated that the wettability of carbon black, CB, can be enhanced by applying the electrocapillary rise wetting, ECRW. Experimentally, an electrostatic generator was employed to assis the common capillary rise by providing varable electric voltages meanwhile four polar and non‐polar solvents were used as probes to wet CB, respectively. The adsorption of polar water and formamide were found to enhance with the voltage increase, while the adsorption of non‐polar hexane and diiodomethane were found always in stable obviously ignoring the voltage variety. The polar solvents‐based contact angles were reduced with the voltage increase leading the enhancement of the wettability and surface free energy of CB. The reason was due to the voltage increase caused the Lewis acid‐base interactions strongly occurring between the polar groups of solvent and CB.