Abstract Herein, we report a transition-metal-free organophotocatalytic strategy for the deoxygenative formation of C(sp3)–N bonds from readily available alcohols. The method employs diaryl ketone O-aroyl oximes as bifunctional reagents, serving as both radical precursors and nitrogen sources. Under mild visible-light irradiation, primary, secondary, and tertiary alcohol-derived xanthates are efficiently converted to imines with broad functional group tolerance. The protocol is practical, enabling gram-scale synthesis, one-pot imidation, and late-stage functionalization of complex molecules such as quinidine. Mechanistic studies indicate a radical pathway mediated by photocatalyst-induced energy transfer.