GRAPHICAL ABSTRACT Light alkanes (C₁-C₁₀) and simple aromatics are derived from desirable crude energy feedstock but present challenging cases for C–H functionalization purposes. This article reviews efforts to mediate C–N bond construction from these abundant sources to generate commodity chemicals of high industrial value. The nitrogen-group donors considered are largely limited to metal-bound or diffusively free nitrenes, nitrenoids, and amides/imides engaged in catalytic or stoichiometric intermolecular reactions. Both synthetic protocols and mechanistic studies are discussed to illustrate the current status of a rapidly developing field that is still in need of significant improvements to effect reactive and selective processes.