Vanadium oxides (V3O7) have been used as electrode materials for supercapacitor applications because of its multiple oxidation states. V3O7 nanoparticles were coated on reduced graphene oxide (rGO) from a peroxovanadate-rGO composite by thermal microexplosive decomposition method. These V3O7 decorated rGO were made composite with the flexible multi redox conducting polymer (Polyaniline). The performance of the composite materials as electrode for supercapacitors was analyzed in a 3-electrode cell, obtaining a specific capacitance of about 579 F g−1 at 0.2 A g−1 specific current. Cycling stability is one of the main barriers noticed in V3O7, which limits the practical performance of supercapacitors. This is overcome by modifying V3O7 with rGO and polyaniline composites which produces good electrical contact resulting in higher capacitances and enhanced cycling stability when compared to pristine V3O7. A superior electrochemical performance and ultra-long cyclic stability of 94% over 2500 cycles was obtained through these developed electrodes.