The excellent properties of metallic glass (MG) films make them perfect candidates for the use in miniature systems and tools. However, their high coefficients of friction (COFs) and poor wear resistance considerably limit their long-term performance in nanoscale contact. We report the fabrication of a MG/graphene multilayer by the repeated deposition of Cu50Zr50 MG with alternating layers of graphene. The microstructure of the multilayer was characterized by the transmission electron microscopy (TEM). Its mechanical and nanotribological properties were studied by nanoindentation and nanoscratch tests, respectively. A molecular dynamics (MD) simulation revealed that the addition of graphene endowed the MG with superelastic recovery, which reduced friction during nanoscratching. In comparison with the monolithic MG film, the multilayer exhibited improved wear resistance and a low COF in repeated nanowear tests owing to the enhanced mechanical properties and lubricating effect caused by the graphene layer. This work is expected to motivate the design of other novel MG films with excellent nanowear properties for engineering applications.