Activated carbon materials have been studied extensively as electrode materials for supercapacitors (SCs), but their poor capacitance and energy density have hampered their growth. We present a one-step synthesis of a ternary boron-nitrogen-phosphorous-doped carbon (BNPC) from biomass hemp fibre to determine its electrochemical hydrogen storage ability using SC applications. FESEM micrographs reveal mixed morphologies like square, diamond and cylindrical-shaped nanosheets, confirming the hetero-atom doping into the carbon skeleton. The optimized BNPC electrode delivers a half-cell specific capacitance and hydrogen-storage capacity of 520 Fg-1 (1 Ag-1) and 360 mAhg−1 (10 mVs−1), respectively. To demonstrate the practicability of the as-prepared BNPC electrode, a symmetric pouch-cell supercapacitor device was assembled which exhibits a full-cell specific capacitance of 262.56 Fg-1 at 1 Ag-1 and a specific energy of ~118 Wh kg−1 at a specific power of ~5759 Wkg-1 with an operating potential window of 1.8 V and 99.7% capacitance retention over 10,000 cycles. This excellent electrochemical performance can be ascribed to the synergetic properties of fast-electrolyte-ion diffusion due to the doping of heteroatoms into the carbon matrix, high conductivity and high specific surface area and effective microporosity of BNPC (1555.5 m2g-1). Also, the chemical stability of the BNPC materials, was investigated with density functional theory (DFT)-single point calculations, where the least molecular orbital energy gap was obtained by the BNPC, which confirms its structural stability. Thus, the prepared ternary BNP-doped carbon derived from biomass has provided a new direction to enhance the electrochemical energy storage potential. © 2021 Hydrogen Energy Publications LLC