photoinduced acylation of N‐heterocycles is explored. This visible‐lighttriggered reaction occurs not only under extremely mild reaction conditions, but also does not require the presence of a photosensitizer. The mechanistic studies suggest formation of EDA complexes prompt to harness the energy from visible‐light. Compatibility with a large panel of α‐keto acids as acyl precursors and an array of N‐heterocycles