The selective cleavage of N-O(alkyl) bonds in acyclic and cyclic Weinreb amides is central to a plenum of enabling technologies in contemporary synthesis. Despite the lability of the bond, metal-based SET protocols continue to dominate the arsenal of methods typically employed. This often presents compatibility issues that limit functional group tolerance. To provide a mild, light-enabled alternative, a mechanism-guided approach based upon PET and ConPET platforms has been developed that harnesses anthracene and 4CzIPN as efficient organophotocatalysts. We demonstrate that the process is redox neutral through the formation of acylated amino aldehydes from cyclic substrates, and establish that amidyl radical formation is not operational. Inspired by Emil Fischer´s synthesis of aminoacetaldehyde, a series of homologated aminoaldehydes have been prepared from simple heterocyclic precursors. Finally, the method has been leveraged to generate highly selective dopamine D3 receptor ligands and chiral 1,3-diamines. Given the popularity of linear ambiphilic derivatives in bioactive molecule design, notably in PROTAC molecules, it is envisaged that this mild N-O bond cleavage protocol will be enabling.