Graphene is the front-runner of the two-dimensional (2D) material family. Despite its remarkable properties and many promising studies in the last two decades, it is still difficult to envision a future where graphene will take the place of silicon in our technological world. On the other hand, combining graphene with the current complementary metal–oxide–semiconductor (CMOS) technology could open up avenues for the realization of novel device architectures with compelling properties. At this aim, we study the properties of graphene when it is interfaced with conventional bulk semiconductors and CMOS-compatible substrates.