Supplementary InformaƟon (ESI) available: SEM and TEM images, the porous structure parameters, XRD patterns, electrochemical capacitive performances using a two-electrode and a three-electrode cell.. See Nitrogen-and oxygen-enriched hierarchical porous carbon fiber was fabricated by the phase-separable wet-spinning and the subsequent chemical activation of polyacrylonitrile (PAN) precursor. The wet-spinning could readily offer an interpenetrating 3D meso-/macro-porous network owing to the phase-separation of PAN in the coagulation bath (DMSO/ H2O), caused by the different solubility of PAN in DMSO and H2O, and the different content of PAN in fiber and the coagulation bath. The later chemical activation introduced abundant small-sized nanopores within the meso-/macroporous network skeleton. The obtained hierarchical porous carbon fiber exhibited high specific surface area of 2176.6 m 2 g -1 , large pore volume of 1.272 cm 3 g -1 , and was highly doped by heteroatoms of nitrogen and oxygen. When it was used as supercapacitor electrodes, high performance of reversible specific capacitances of 329 F g -1 at 0.1 A g -1 and 223 F g -1 at 20 A g -1 as well as the capacitance retention of 97.6% after 2000 cycles were achieved in a two-electrode cell.