Abstract Recent advances in photocatalytic organic transformations have enabled new bond formations that are otherwise challenging under thermal reaction conditions. Among these, significant progress has been achieved especially in amination reactions by harnessing the reactivity of nitrogen‐centered radicals or organic nitrene species, generated from various prefunctionalized amino group precursors, through photoinduced single‐electron transfer (SET) or triplet–triplet energy transfer (TTEnT). Although plausible mechanisms leading to the reactive nitrogen‐centered intermediate have been proposed, a detailed depiction of the electron flow during the photoinduced process would be highly intriguing. In this study, we employed computational intrinsic bond orbital (IBO) analysis to illustrate the electron relocations during the activation of several types of aminating precursors into nitrogen‐centered radicals or organic nitrenes. Our quantum chemical investigations provide critical mechanistic insights into the nitrogen‐centered reactive intermediate formation, offering foundations for designing photocatalytic amination strategies.