A supercapacitor is an electrical energy storage system with high power output. With worldwide awareness of sustainable development, developing cost-effective, environmentally friendly, and high-performance supercapacitors is an important research direction. The use of sustainable components like wood biochar in the electrode materials for supercapacitor uses holds great promise for sustainable supercapacitor development. In this study, we demonstrated a facile and powerful approach to prepare meso-microporous carbon electrode materials for sustainable and high-performance supercapacitor development by electrospinning polyacrylonitrile (PAN) with F-treated biochar and subsequent aerogel construction followed by stabilization, carbonization, and carbon activation. The resultant carbon nanofibrous aerogel electrode material (ENFA-FBa) exhibited exceptional specific capacitance, attributing to enormously increased micropore and mesopore volumes, much more activated sites to charge storage, and significantly greater electrochemical interaction with electrolyte. This electrode material achieved a specific capacitance of 407 F/g at current density of 0.5 A/g in 1 M H2SO4 electrolyte, which outperformed the state-of-the-art specific capacitance of biochar-containing electrospun carbon nanofibrous aerogel electrode materials (<300 F/g). A symmetric two-electrode cell with ENFA-FBa as electrode material showed an energy density of 11.2 Wh/kg at 125 W/kg power density. Even after 10,000 cycles of charging-discharging at current density of 10 A/g, the device maintained a consistent coulombic efficiency of 53.5% and an outstanding capacitance retention of 91%. Our research pointed out a promising direction to develop sustainable electrode materials for future high-performance supercapacitors.