Oxygen-rich porous carbon is of great interest for energy storage applications due to its improved local electronic structures compared with unmodified porous carbon. However, a tunable method for the preparation of oxygen-rich porous carbon with a special microstructure is still worth developing. Herein, a novel modification of porous carbon with different microstructures is facilely prepared via low-temperature solvothermal and KOH activation methods that employ the coal tar and eight substances, such as cellulose as carbon source and modifier, respectively. By testing the yield, surface group structure, lattice structures, morphology, thermal weight loss, and specific capacitance of carbonaceous mesophase, cellulose–hydrochloric acid is identified as the additive for the preparation of oxygen-rich coal tar-based porous carbon. The obtained porous carbon displays a specific surface area of up to 859.49 m2 g− 1 and an average pore diameter of 2.39 nm. More importantly, the material delivers a high capacity of 275.95 F g− 1 at 0.3 A g− 1 and maintains a high capacitance of 220 F g− 1 even at 10 A g− 1. When in a neutral electrolyte, it can still retain a reversible capacity of 236.72 F g− 1 at 0.3 A g− 1 and 136.79 F g− 1 at 10 A g− 1. This work may provide insight into the design of carbon anode materials with high specific capacity.