Nitrogen-containing compounds are widely present in both natural products and synthetic compounds, for example, they show up within functional materials, top-selling drugs, as well as bioactive molecules. Although significant progresses have been developed in the direct functionalization of simple hydrocarbons, direct incorporation of N-atoms into the simple substrates via C–H and/or C–C bond cleavage remains challenging due to the inert chemical bonds and the unstable character of some N-sources under oxidative conditions. In this presentation, our recent progress on the direct nitrogenation of simple hydrocarbons will be introduced.