Electrochemically active bi-metallic nano-ensemble, Graphene-Cobalt-Nickel (G-Co-Ni) is proposed as the electro-catalyst for direct oxidation of BH4- ions. Three nano-hybrid electro-catalysts namely Graphene-Cobalt (G-Co), Graphene-Nickel (G-Ni) and Graphene-Cobalt-Nickel (G-Co-Ni) are synthesized and characterized using XRD, FTIR, Raman's spectroscopy, SEM, HRTEM, EDAX and mass absorption spectroscopy. The electro-catalytic activity of the synthesized catalysts towards the oxidation of BH4- ions was investigated by means of cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Among the different electro-catalysts G-Co-Ni (�4.5:1:1 weight ratio) exhibits the highest value of electroactive surface area (ESA = 518.6 m2/gm). G-Co-Ni shows enhanced mass specific activity (msa: 750-900 A g-1) towards the direct oxidation of BH4- ions and oxidation of H2 generated by catalytic hydrolysis of BH4- ions comparing with G-Ni (msa: 130-160 A g-1) and G-Co (msa: 120-130 A g-1) catalysts. The enhanced electro-catalytic activity is attributed to the increased number of reaction sites and pathways of electron transfer through graphene supported bimetals. © 2014 Hydrogen Energy Publications, LLC.