<p>Anthracite is one of the highest metamorphic coal with fixed carbon content of over 90%, regarded as a high-quality carbon source for preparing activated carbon (AC). The ACs derived from various coal macerals has significant structure and property differences. This work provides a new sythesis strategy of highly capacitive nitrogen-doped AC (NAC) using maceral-based polyaniline as the starting material via chemical activation. Two macerals of vitrinite-rich group and inertinite-rich group were first separated from Taixi anthracite via heavy-liquid flotation method. Maceral-based polyaniline precursors were then constructed via in-situ polymerization. After the KOH chemical activation of precursors, a series of NAC materials was eventually harvested with the interpenetrating well-developed pore structure including large specific surface area, high mesopore ratio and appropriate nitrogen doping. Compared with the NAC prepared from unseparated anthracite, the NAC-2:3-I derived from inertinite-rich group exhibited higher specific capacitance, rate capability and cycling stability due to larger surface area of 3462 m²&#xa0;g⁻¹, higher mesopore ratio of 66.4%, average pore size of 2.4&#xa0;nm, and 0.64 wt% nitrogen incorporation mainly in the form of pyridinic N and pyrrolic N. Its specific capacitance of single electrode reached 479 F g⁻¹ at 1 A g⁻¹, and still maintained 352 F g⁻¹ at 50 A g⁻¹. The assembled NAC-2:3-I//AC symmetric supercapacitor had a large specific capacitance of 195 F g⁻¹ at 1 A g⁻¹, high capacitance retention of 99% after 10,000 cycles at 5 A g⁻¹, and high energy density of 20 Wh kg⁻¹ at a power density of 550 W kg⁻¹. </p>