Sustainable biomass-derived porous carbons demonstrate excellent capacitive properties owing to their heteroatom-rich nature and distinct textural feature. Herein, a series of nitrogen-/phosphorus-/oxygen-containing microporous carbons (CWWN/ P/O-MPCs) have been successfully fabricated by etching in H2O2 solution, pre-treatment of camphor wood wastes with KOH solution and subsequent carbonization. As an electrode material for supercapacitors, the typical microporous carbon (CWW-N/P/O-MPCs-0.5) exhibits a remarkably high specific capacitance of 245 F g− 1 at 0.5 A g− 1, corresponding to an impressively large volumetric capacitance of 208 F m− 3, and excellent long-term stability over 10,000 cycles. The excellent electrochemical performance can be ascribed to the optimal combination of heteroatom groups and ultrafine micropores.