The importance of anion–π interactions as a driving force for chemical and biological processes is increasingly being recognized. In this communication, we describe for the first time its key participation in light‐induced reactions. We show, in particular, how transient complexes formed through noncovalent anion–π interactions between electron‐poor N‐aryloxyamides and multiply‐charged anions (such as carbonate or phosphate) can undergo facile light‐promoted N−O cleavage, affording amidyl radicals that can subsequently be trapped by (hetero)aromatics.