Graphene based nanocomposites have been investigated intensively, as electrode materials for energy storage applications. In the current work, a graphene-CNT-MnO2-PANI (GCM@PANI) nanocomposite has been synthesized on 3D graphene grown on nickel foam, as a highly efficient binder free electrode material for supercapacitors. Interestingly, the specific capacitance of the synthesized electrode increases up to the first 1500 charge-discharge cycles, and is thus referred to as an electrode activation process. The activated GCM@PANI nanocomposite electrode exhibits an extraordinary galvanostatic specific capacitance of 3037 F g-1 at a current density of 8 A g-1. The synthesized nanocomposite exhibits an excellent cyclic stability with a capacitance retention of 83% over 12 000 charge-discharge cycles, and a high rate capability by retaining a specific capacitance of 84.6% at a current density of 20 A g-1. The structural and electrochemical analysis of the synthesized nanocomposite suggests that the astonishing electrochemical performance might be attributed to the growth of a novel PANI nanoparticle layer and the synergistic effect of CNT/MnO2 nanostructures.