Three-dimensional (3D) hierarchically porous carbons have been extensively investigated as their large surface area and facile ion transport can provide high-performance in energy applications. Here we report new hierarchically porous carbon materials based on a polymer of intrinsic microporosity (PIM composed of ethanoeanthracene (EA) by Tröger base (TB) components (PIM-EA-TB)), for use in high-performance supercapacitor electrodes. Hierarchically structured carbon was prepared from nonsolvent-induced phase separation (NIPS) and subsequent carbonization. The intrinsic micropores of PIM-EA-TB and meso- and macro-pores formed via the NIPS process imbue the resulting carbon material with a hierarchical porous architecture with an exceptionally high surface area of 1966 m2 g−1 and a high electrical conductivity of 83.6 S cm−1. This well-organized structure provides pathways for efficient charge transportation, giving it a high specific capacitance of 46 F g−1 at 1 A g−1 and an excellent specific energy of 17 W h kg−1 at a specific power of 1 kW kg−1.