Over the past few years, there has been a growing potential use of graphene and its derivatives in several biomedical areas, such as drug delivery systems, biosensors, and imaging systems, especially for having excellent optical, electronic, thermal, and mechanical properties. Therefore, nanomaterials in the graphene family have shown promising results in several areas of science. The different physicochemical properties of graphene and its derivatives guide its biocompatibility and toxicity. Hence, further studies to explain the interactions of these nanomaterials with biological systems are fundamental. This review has shown the applicability of the graphene family in several biomedical modalities, with particular attention for cancer therapy and diagnosis, as a potent theranostic. This ability is derivative from the considerable number of forms that the graphene family can assume. The graphene-based materials biodistribution profile, clearance, toxicity, and cytotoxicity, interacting with biological systems, are discussed here, focusing on its synthesis methodology, physicochemical properties, and production quality. Despite the growing increase in the bioavailability and toxicity studies of graphene and its derivatives, there is still much to be unveiled to develop safe and effective formulations.