Graphene has attracted tremendous research interest in recent years, owing to its exceptional properties. The scaled-up and reliable production of graphene derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), offers a wide range of possibilities to synthesize graphene-based functional materials for various applications. This critical review presents and discusses the current development of graphene-based composites. After introduction of the synthesis methods for graphene and its derivatives as well as their properties, we focus on the description of various methods to synthesize graphene-based composites, especially those with functional polymers and inorganic nanostructures. Particular emphasis is placed on strategies for the optimization of composite properties. Lastly, the advantages of graphene-based composites in applications such as the Li-ion batteries, supercapacitors, fuel cells, photovoltaic devices, photocatalysis, as well as Raman enhancement are described (279 references).