Activated carbon (AC) has attracted tremendous research interest as an electrode material for supercapacitors owing to its high specific surface area, high porosity, and low cost. However, AC-based supercapacitors suffer from limited rate performance and low power density, which mainly arise from their inherently low electrical conductivity and sluggish ion dynamics in the micropores. Here, we propose a simple yet effective strategy to address the aforementioned issue by nitrogen/fluorine doping and enlarging the micropore size. During the treatment, the decomposition products of NH4F react with the carbon atoms to dope the AC with nitrogen/fluorine and simultaneously enlarge the pores by etching. The treated AC shows a higher specific surface area of 1826 m2 g−1 (by ~ 15%), more micropores with a diameter around 0.93 nm (by ~ 33%), better wettability (contact angle decreased from 120° to 45°), and excellent electrical conductivity (96 S m−1) compared with untreated AC (39 S m−1). The as-fabricated supercapacitors demonstrate excellent specific capacitance (26 F g−1 at 1 A g−1), significantly reduced electrical resistance (by ~ 50%), and improved rate performance (from 46.21 to 64.39% at current densities of 1 to 20 A g−1). Moreover, the treated AC-based supercapacitor achieves a maximum energy density of 25 Wh kg−1 at 1000 W kg−1 and a maximum power density of 10,875 W kg−1 at 15 Wh kg−1, which clearly outperforms pristine AC-based supercapacitors. This synergistic treatment strategy provides an effective way to improve the rate performance and power density of AC-based supercapacitors.