Oximes are widely used precursors in synthetic chemistry due to their broad availability and versatile chemical properties, in which N─O bond fragmentation represents a key reactivity mode. However, these transformations typically require the use of oxygen-protected oximes, and a general strategy to directly utilize free oximes remains challenging due to their vulnerability to side reaction pathways, rendering low tendency towards N─OH bond cleavage. Here a unified platform is reported to achieve direct cyclization of unprotected oximes with enals, as well as other coupling partners through dual copper/organophotoredox catalysis under green light irradiation. This protocol enables concurrent activation of both N─OH and α-C(sp