Graphene-family nanomaterials (GFNs) possess mechanical stiffness, optical properties, and biocompatibility making them promising materials for biomedical applications. However, to realize the potential of graphene in biomedicine, it must overcome several challenges that arise when it enters the body’s circulatory system. Current research focuses on the development of tumor-targeting devices using graphene, but GFNs accumulated in different tissues and cells through different pathways, which can cause toxic reactions leading to cell apoptosis and body dysfunction when the accumulated amount exceeds a certain limit. In addition, as a foreign substance, graphene can induce complex inflammatory reactions with immune cells and inflammatory factors, potentially enhancing or impairing the body’s immune function. This review discusses the biomedical applications of graphene, the effects of graphene materials on human immune function, and the biotoxicity of graphene materials.