The preparation of electrode materials with superior electrochemical performance and excellent mechanical properties are essential for the fabrication of flexible supercapacitors. However, the compatibility of the porosity and flexibility for the electrode materials remains challenging. Herein, free-standing porous coaxial carbon nanofiber (PCCNF) membranes with large specific surface area (648 m2 g−1) and suitable pore size distribution were fabricated by a facile coaxial electrospinning technique and template method. PCCNF possesses superb capacitance of 261 and 48 F g−1 (1 A g−1) in three-electrode and two-electrode system, respectively, result in remarkable energy density (48.6 ± 3 Wh kg−1) and power density (67.5 ± 1 Wh kg−1). Moreover, supercapacitor devices based on PCCNF show superb flexibility as well as excellent electrochemical and mechanical stability. PCCNF-based high performance supercapacitors may be suitable for flexible electronic energy storage devices.