Electronically conducting polymers (ECPs)/carbon nanomaterialbased polyaniline electrodes have received great interest in the field of supercapacitors due to their high specific capacitance, good electronic conductivity, good mechanical strength, good chemical and electrochemical stabilities, etc. Among the various available ECPs, they have received much importance due to their excellent electrochemical performances. Herein, we report a facile synthesis of a PANI-grafted graphene oxide (GO)-azopyridine (Azo) (PANI/GO-Azo) nanocomposite and use it as electrodes for fabricating supercapacitors. The azo units present in the nanocomposite act as a spacer between PANI and GO. The interfacial polymerization method is adopted for the synthesis of PANI/GO-Azo nanocomposites. The PANI/ GO-Azo nanocomposite electrode exhibits a gravimetric capacitance of 426 F g −1 at a current density of 0.25 A g −1 in 1 M H 2 SO 4 (aqueous) electrolyte. The electrode possesses good cycling stability of more than 5000 cycles with a Coulombic efficiency of 98.5%. An asymmetric supercapacitor fabricated with PANI/GO-Azo as the positive electrode and activated carbon as the negative electrode delivers an energy density of 12.45 W h kg −1 with a power density of 274.9 W kg −1 . This study proclaims that the PANI/GO-Azo nanocomposite electrode is highly promising for next-generation supercapacitors.