Highly polar CN functional groups on polyacrylonitrile (PAN) facilitate strong hydrogen bonding and dipole-dipole interactions with hydroxyl groups on the surfaces of active materials and current collectors. Here we report that the strong interaction between PAN and carbon black (CB) particles facilitates a uniform distribution of CB particles within the electrode and forms a well-connected conductive network on the surface of active material particles. This significantly enhances electron transport within the electrode, offering superior rate performance and cycling stability beyond traditional binders like polyvinylidene fluoride (PVDF). Activated carbon (AC) electrodes containing 7.70 wt.% PAN binder (AC-7.7PAN) deliver areal capacitances over 0.60 F cm⁻2 at a scan rate of 500 mV s⁻1, and exhibits a high gravimetric energy density (Eg) of 26.20 Wh kg⁻1 and high areal energy density (Ea) of 0.33 mWh cm⁻2 at a current density of 1 A g⁻1. An AC-7.7PAN coin-cell supercapacitor maintains up to 62 % of its initial capacitance at a scan rate of 200 mV s⁻1, while a controlled AC-7.7PVDF coin-cell keeps only 37 % under the same conditions. The AC-7.7PAN coin-cell retains 91 % of its capacity even after 50,000 charge/discharge cycles at a constant current of 5 A g⁻1. The ability of PAN to evenly distribute conductive agents might be attractive for other power-type electrochemical electrodes, for which effective electron transport are extremely required.