Relying on the excellent physical and chemical properties, graphene materials have attracted great attention in the biomedical field and shown broad application prospects. It needs to be noted that when graphene materials are used for bio-applications, such as drug delivery, medical sensing and bioimaging, they will interact inevitably with various proteins and result in the changing of their own properties as well as the variation of proteins’ conformation and functions. Therefore, a lot of studies have been carried out to investigate the interactions between graphene materials and protein molecules, which is of vital importance for understanding and evaluating the biological effects of graphene materials. In this content, the representative scientific researches on this topic are reviewed. The molecular mechanisms of the interactions between various materials of the graphene family and proteins are summarized, and the newly developed biotechnologies based on the graphene material / protein interactions are introduced. Finally, some personal perspectives of the further research directions in this field are presented.