Identifying catalytically active sites in graphene-based catalysts is critical to improved oxygen reduction reaction (ORR) electrocatalysts for fuel-cell applications. To generate abundant active edge sites on graphene-based electrocatalysts for superior electrocatalytic activity, rather than at their basal plane, has been a challenge. A new type of ORR electrocatalyst produced using fluidization process and based on a three-dimensional hybrid consisting of horizontally-aligned carbon nanotube and graphene (CNT-G), featured abundant active edge sites and a large specific surface area (863 m2 g−1). The Pt-doped CNT-G exhibited an increase of about 55% in mass activity over the state-of-the-art commercial Pt/C and about 164% over Pt/N-graphene in acidic medium, and approximately 54% increase in kinetic limiting current than the Pt/C at low overpotential in alkaline medium. The higher mass activity indicates that less Pt is required for the same performance, reducing the cost of fuel cell electrocatalyst. In hydrogen evolution reaction (HER), both the metal-free CNT-G and Pt/CNT-G exhibited superior electrocatalytic activity compared to N-doped graphene and commercial Pt/C, respectively.