A photoinduced nickel-catalyzed reductive carbonylative coupling from organohalides and N-(acyloxy)phthalimide esters with phenyl formate as the carbonyl source has been developed. This reaction could perform smoothly under mild conditions, and a series of aryl−alkyl and alkyl−alkyl unsymmetrical ketones were produced without the need of stoichiometric metal reductants. Mechanistic studies indicate that this reaction was initiated from radical capture by Ni(I)carbonyl species and subsequent rapid carbonyl insertion.