A porous carbon fiber derived from polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) is developed for zinc-ion hybrid supercapacitors (ZHSs). The fiber is prepared via a blend electrospinning and hydrothermal selective PVP removal strategy. This method avoids cross-linking between PVP and PAN during stabilization, enabling the formation of hierarchical porous structures. The sufficient micropores provide space for Zn²⁺ storage, while the mesopores facilitate fast ion transfer, resulting in high specific capacity and high-rate performance. The optimal PVP/PAN-derived porous carbon fiber (PVP-PANC-0.8) exhibits a specific capacity of 208 mAh·g⁻¹, a high rate capability of 49.5% from 0.5 to 5 A·g⁻¹, and 72.25% capacity retention after 10,000 cycles at 0.5 A·g⁻¹. The preparation involves electrospinning PVP/PAN blend solutions, followed by hydrothermal treatment to remove PVP, and subsequent carbonization. The PVP/PAN ratio is adjusted to control the pore structure and optimize the performance. The cathode is fabricated by mixing PVP-PANC-x with acetylene black and PVDF, and coating on a stainless steel mesh. Electrochemical tests, including cyclic voltammetry, EIS, GCD, and cycle life tests, confirm the excellent performance of the PVP-PANC-0.8 cathode. The hierarchical porous structure of the carbon fiber is crucial for achieving high electrochemical performance in ZHSs. This study provides an effective strategy for designing porous carbon fibers with tailored microstructures for ZHSs.A porous carbon fiber derived from polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) is developed for zinc-ion hybrid supercapacitors (ZHSs). The fiber is prepared via a blend electrospinning and hydrothermal selective PVP removal strategy. This method avoids cross-linking between PVP and PAN during stabilization, enabling the formation of hierarchical porous structures. The sufficient micropores provide space for Zn²⁺ storage, while the mesopores facilitate fast ion transfer, resulting in high specific capacity and high-rate performance. The optimal PVP/PAN-derived porous carbon fiber (PVP-PANC-0.8) exhibits a specific capacity of 208 mAh·g⁻¹, a high rate capability of 49.5% from 0.5 to 5 A·g⁻¹, and 72.25% capacity retention after 10,000 cycles at 0.5 A·g⁻¹. The preparation involves electrospinning PVP/PAN blend solutions, followed by hydrothermal treatment to remove PVP, and subsequent carbonization. The PVP/PAN ratio is adjusted to control the pore structure and optimize the performance. The cathode is fabricated by mixing PVP-PANC-x with acetylene black and PVDF, and coating on a stainless steel mesh. Electrochemical tests, including cyclic voltammetry, EIS, GCD, and cycle life tests, confirm the excellent performance of the PVP-PANC-0.8 cathode. The hierarchical porous structure of the carbon fiber is crucial for achieving high electrochemical performance in ZHSs. This study provides an effective strategy for designing porous carbon fibers with tailored microstructures for ZHSs.