Large accessible surface area, facile pore engineering, and high electrical conductivity are highly desirable properties of efficient electrode materials. Herein, porous carbon fibers with a graphitic carbon skeleton and amorphous carbon body are successfully synthesized from directly carbonized polyacrylonitrile (PAN)/FeCl3 electrospun fibers via in situ catalytic graphitization and subsequent chemical activation. Due to the graphitic carbon skeleton, which facilitates fast electron transfer, and porous carbon body, which gives a large specific surface area for charge accumulation and fast ion diffusion, optimal porous graphitic carbon fibers are developed that exhibit a fast-charging electrochemical performance with a capacitance of 165 F g(-1) at high current densities of 300 A g(-1) in an alkaline electrolyte. These findings can prove to be beneficial for realizing a supercapacitor with rapid charging and discharging ability at high current densities.