Here, we present a metal-free photosensitized three-component reaction for the carboimination of alkenes based on oxime carbonates. Homolysis of oxime carbonates via light-mediated energy transfer enables the simultaneous generation of iminyl radicals and alkoxycarbonyloxyl radicals. The alkoxycarbonyloxyl and alkoxy radicals can act as an effective hydrogen atom transfer reagent, abstracting hydrogen atoms from alkanes and aldehydes, silanes, and phosphine oxide. This strategy exhibits broad functional group tolerance under mild reaction conditions, further broadening the diversity of alkene carboimination.