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We report the microstructure, electrical and electrochemical properties of hybrid nanofibers composed of polyacrylonitrile (PAN)/lignin-derived carbon nanofibers and LaMnO3-based inorganic nanofibers for advanced applications as free-standing and binder-free electrode materials of energy storage devices. For this purpose, hybrid nanofibers are fabricated via dual-electrospinning technique and following heat-treatment at different temperatures of 700–1000 °C for simultaneous carbonization and calcination. The SEM, EDS, and XPS analyses reveal that the carbon content in the hybrid nanofibers increases with increasing the heat-treatment temperature and that La and Mn elements are dispersed uniformly over the hybrid nanofibers. The hybrid nanofibers heat-treated at 900 and 1000 °C have a high electrical conductivity of ~ 0.22 S/cm and ~ 0.35 S/cm, respectively. Accordingly, a symmetric two-electrode supercapacitor based on hybrid nanofibers heat-treated at 1000 °C is characterized to have excellent electrochemical performance such as specific capacitance of ~ 95.2 F/g at 1 A/g, power density of 667 W/kg, energy density of 17.6 Wh/kg, and capacitance retention of ~ 97% after 2000 cycles. The results denote that PAN/lignin and LaMnO3-based hybrid nanofibers can be utilized as self-supporting high-performance electrode materials for advanced energy storage devices. [ABSTRACT FROM AUTHOR]