The direct functionalization of Si–H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhI═NTs to the Si–H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si–NH moieties in the first example of this transformation. The process tolerates other functionalities in the substrate such as several C–H bonds and alkyne and alkene moieties directly bonded to the silicon center. Density functional theory (DFT) calculations provide a mechanistic interpretation consisting of a Si–H homolytic cleavage and subsequent rebound to the Si-centered radical.