With the continuous deepening of research on nanomaterials, it has been applied in a wide range of technical fields, and has great potential to support new discoveries in basic sciences. Among them, nanomaterials composed of single elements are of particular interest because they are tractable and readily available in synthesis. Two-dimensional (2D) nanomaterials from Group VA single-element (including black phosphorus, arsenene) have broad application prospects in biological applications such as bioimaging, drug delivery, and diagnostic therapy due to their excellent physical, chemical, electronic, and optical properties. This review summarizes the general properties, synthesis, and modification methods of group VA single-element 2D nanomaterials, and then focuses on their various biomedical applications. Finally, challenges and future prospects of these nanomaterials in the field of biomedicine are discussed.