The PVDF (Poly-Vinyl-difloride) membrane modified with Bismuth oxide (β-Bi2O3)/Bismuth Ferrite (BiFeO3) p-n heterojunction synthesized via hydrothermal process to explore its energy storage and conversion applications. The PVDF-Bi2O3/BiFeO3 nanocomposites (NCs) prepared in this study were subjected to analysis using PXRD, FTIR, UV-Vis DRS, FE-SEM with EDX, TEM, and transient photocurrent response techniques, individually. The as-prepared materials were evaluated for their photocatalytic performance in the visible light-induced degradation of Methylene Blue (MB) and Rhodamine-B (RhB) dyes. The photocatalytic performance demonstrates degradation efficiencies of 95% for MB dye and 83% for RhB dye when utilizing the PVDF-β-Bi2O3@BiFeO3 nanocatalyst. The enhancement in the photocatalytic performance of the PVDF-Bi2O3/BiFeO3 heterojunction was a result of improved visible light absorption, suppression of photogenerated electron-hole pair recombination, accelerated separation and migration of photogenerated charges. The capacitance behavior of PVDF-β-Bi2O3@BiFeO3 is significantly higher than β-Bi2O3@BiFeO3 in 3 M KOH solution which has specific capacitance of 300 F g−1at 1 A g−1 of current density and fabricated a symmetric device has10.08 Wh kg−1 and 999.39 W kg−1 specific energy and specific power at 0.5 A g−1 of current density with the 88.7% of capacitance retention and 94.12% of coulombic efficiency up to 10000 cycles. © 2024 Elsevier B.V., All rights reserved.