Graphene is considered as one of the most promising materials in a wide range of applications because of its outstanding electronic, optical, thermal, and mechanical properties. Given its large specific surface area, two-dimensional structure, facile decoration, and high adsorption capacity, numerous graphene-based nanomaterials with unprecedented characteristics have been designed, prepared, and applied in catalysis. In this article, we first reviewed common synthetic methods to prepare graphene-based catalysts followed by critical comments and possible solutions. We then briefly summarized the characterization techniques that were relevant to catalysis applications and their applications in energy conversion, environmental protection, and several other typical fields. Finally, we discussed the challenges and opportunities for the future development of graphene-based nanomaterials in sustainable catalysis. This review provides key information to the catalysis community to design and fabricate graphene-based novel nanomaterials with great performance.