The paper presents the development of a porous carbon fiber derived from polyvinylpyrrolidone (PVP) and polyaniline (PAN) for zinc-ion hybrid supercapacitors (ZHSs). The PVP/PAN blend electrospinning technique and a hydrothermal selective PVP removal strategy were employed to create a hierarchical porous structure. This structure, characterized by abundant micropores for Zn²⁺ storage and mesopores for fast ion transfer, enhances the specific capacity and rate performance of ZHSs. The optimized PVP/PAN-derived porous carbon fiber (PVP-PANC-0.8) exhibited a high 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 study highlights the importance of microstructure regulation in carbon fibers for improving the electrochemical performance of ZHSs.The paper presents the development of a porous carbon fiber derived from polyvinylpyrrolidone (PVP) and polyaniline (PAN) for zinc-ion hybrid supercapacitors (ZHSs). The PVP/PAN blend electrospinning technique and a hydrothermal selective PVP removal strategy were employed to create a hierarchical porous structure. This structure, characterized by abundant micropores for Zn²⁺ storage and mesopores for fast ion transfer, enhances the specific capacity and rate performance of ZHSs. The optimized PVP/PAN-derived porous carbon fiber (PVP-PANC-0.8) exhibited a high 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 study highlights the importance of microstructure regulation in carbon fibers for improving the electrochemical performance of ZHSs.