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[Display omitted] • The NB-PCNF and MnO 2 /Co 3 O 4 /NB-PCNF were successfully fabricated via needleless electrospinning. • The co-doping of multiple non-metallic atoms enhances the electrochemical capability of carbon nanofibers. • The heterogeneous structure in MnO 2 /Co 3 O 4 /NB-PCNF can effectively improve the electrical conductivity. • A flexible asymmetric solid-state supercapacitor (FASS-SC) exhibits excellent electrochemical performance. Rational design of an electrode material with high flexibility and electrochemical performance is the key to wearable energy storage devices. Herein, a facile and productive needleless electrospinning method was introduced to prepare self-supported and flexible nanofibrous electrode materials for asymmetric capacitor. The MnO 2 nanoclusters and ZIF67-derived Co 3 O 4 nano-sheets were sequentially deposited on the surface of N, B-doped carbon nanofibers (hetero-junction MnO 2 /Co 3 O 4 /NB-PCNF). Attributing to the constructed multi-pathway for redox reactions on electrode, the specific capacitance of NB-PCNF and MnO 2 /Co 3 O 4 /NB-PCNF can reach up to 204.2F/g and 141.43F/g at a small current density of 0.1 A/g, respectively. In long-term cycling tests, the electrode materials exhibited excellent cycling stability and good rate capability. The electrodes were assembled with Potassium-ion hydrogel electrolyte to form a flexible asymmetric solid-state supercapacitor (FASS-SC). FASS-SC can reach a voltage window of 1.6 V. It provided 28.2 W h/kg at an energy density of 600 W/kg and a specific capacitance retention of 94.18 % after 10,000 cycles. The FASS-SC offers new research ideas for future flexible devices and wearable technologies. [ABSTRACT FROM AUTHOR]