Tris(bipyridyl)ruthenium(II) ([Ru(bpy)(3)](2+) : TB(II)) catalyzes oxidative coupling of enamines and aldehydes with 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) under irradiation of visible light to afford alpha-oxyaminated carbonyl compounds. The visible light irradiation is essential to generate the triplet excited state of *TB(II) which acts as an oxidizing agent. This is a new procedure for radical coupling based on single electron transfer mediated by photoactivated TB.