Oxide nanomaterials have attracted significant attention as energy storage materials. The combination of spinel-perovskite oxides as nanocomposites creates dense oxygen vacancies (VO) at the hetero-interface. VO present in the complex oxides are indispensable for energy conversion applications. Herein, we demonstrated the one pot synthesis of spinel-perovskite NiFe2O4-xLaFeO3 nanocomposite and investigated the phase formation using variable temperature powder X-ray diffraction of the gel precursor. The role of oxygen-vacancy mediated tuneable redox transitions in NiFe2O4-xLaFeO3 nanocomposite has been understood. The anion-intercalation-based pseudocapacitance and the oxygen intercalation have been exploited for high-performance electrochemical energy storage. The NiFe2O4–2LaFeO3 exhibited a high specific capacity of 652 C g−1 at a current density of 2 A g−1. The fabricated NiFe2O4–2LaFeO3||NiCo2O4 asymmetric supercapacitor device (ASC) exhibited excellent cyclability over 20,000 cycles with superior capacity retention and high Coulombic efficiency (92 %) and achieved a high energy density of 42.5 Wh kg−1 at a power density of 1500 W kg−1. The presence of VO and the mixed-valence states of Fe2+/3+ were confirmed by XPS-depth profiling. The tuneable redox transition of Fe2+/3+ and VO contribute to the higher pseudocapacitance response.