The unique properties of two-dimensional structure, great intrinsic carrier, well developed porosity, active surface area, outstanding electronic properties and promising mechanical and thermal stability make graphene as the current support key material in the heterogeneous catalyst system. Accordingly, graphene plays a pivotal role in most heterogeneous catalysts ranging from single to bi-functional, hybrid, oxide and nano systems. This combination also inspires and widens the heterogeneous catalyst application areas, including chemical conversion, photocatalyst, electrochemical sensor, fuel cell, energy storage and others. This review highlights the advantages and limitations of carbon materials as catalyst support materials, addresses recent progress on synthesis routes with technological advances in the characterization of graphene, and follows the properties dependent of graphene as a superior catalyst support material. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.