In this study, we have fabricated the phenolic resin (PR)/polyacrylonitrile (PAN) blend-derived core-sheath nanostructured carbon nanofibers (CNFs) via one-pot solution electrospinning. The obtained core-sheath nanostructured carbon nanofibers were further treated by mixed salt activation process to develop the activated porous CNFs (CNF-A). Compared to pure PAN-based CNFs, the activated PR/PAN blend with PR 20% (CNF28-A)-derived core-sheath nanostructured CNFs showed enhanced specific capacitance of ~ 223 F g⁻¹ under a three-electrode configuration. Besides, the assembled symmetric CNF28-A//CNF28-A device possessed a specific capacitance of 76.7 F g⁻¹ at a current density of 1 A g⁻¹ and exhibited good stability of 111% after 5,000 galvanostatic charge/discharge (GCD) cycles, which verifies the outstanding long-term cycle stability of the device. Moreover, the fabricated supercapacitor device delivered an energy density of 8.63 Wh kg⁻¹ at a power density of 450 W kg⁻¹.