Photoreactions of epoxy ketones, aromatic ketones, haloketones, and aromatic halides with 1, 3-dimethyl-2-phenylbenzimidazoline (DMPBI) were studied. Photoinducedsingle-electron transfer from DMPBI to such substrates initiates the reactions, followed by radical rearrangement and reduction to finally give several reduced products in modest to good yields.