In conclusion, we report a novel photolytic Nickel-catalyzed decarboxylative dehydrogenation toward carbonyl compounds in excellent isolated yields. The protocol is robust across substrates with varying electronic properties, due to the decoupling of the decarboxylation and the oxidation event starting from Mandelic acid derivatives. Ongoing studies in our laboratory are elucidating the mechanistic details, in particular the nickel catalytic cycle. The careful modulation of redox states of nickel catalysts will pave the way for the development of new catalytic dehydrogenation reactivities under free-radical control.