The main graphene‐family materials used in biomedicine include graphene, graphene oxide, and reduced graphene oxide. They have been well documented for their distinctive microstructure and excellent physicochemical properties. Although they also have some shortcomings, such as slow biodegradation and dose‐dependent biotoxicity, these problems can be solved by using them in conjunction with other biomaterials. Silk fibroin (SF), a natural polymer material with many advantageous properties, has been used widely in biomedicine. However, SF requires modification by other biomaterials to improve its mechanical properties and control its degradation rate for further use. In recent years, the combined application of graphene‐family materials and SF has increased gradually, and the effects of it on cell behavior have been preliminary investigated, such as promoting cell adhesion, proliferation, and differentiation. Further studies of the combined use have been conducted in biomedicine, including tissue engineering, biosensor, and other biomedical usage. In this paper, this combined application has been outlined and summarized, and some envisioned challenges and future perspectives have been mentioned. We hope that this review will provide some reference and inspiration for the combined application of graphene‐family materials and SF in biomedicine in the future.