The catalytic hydrogenation activity of the readily prepared, coordinatively saturated cobalt(I) precatalyst, (R,R)-((iPr)DuPhos)Co(CO)(2)H ((R,R)-(iPr)DuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene), is described. While efficient turnover was observed with a range of alkenes upon heating to 100 degrees C, the catalytic performance of the cobalt catalyst was markedly enhanced upon irradiation with blue light at 35 degrees C. This improved reactivity enabled hydrogenation of terminal, di-, and trisubstituted alkenes, alkynes, and carbonyl compounds. A combination of deuterium labeling studies, hydrogenation of alkenes containing radical clocks, and experiments probing relative rates supports a hydrogen atom transfer pathway under thermal conditions that is enabled by a relatively weak cobalt-hydrogen bond of 54 kcal/mol. In contrast, data for the photocatalytic reactions support light-induced dissociation of a carbonyl ligand followed by a coordination-insertion sequence where the product is released by combination of a cobalt alkyl intermediate with the starting hydride, (R,R)-((iPr)DuPhos)Co(CO)(2)H. These results demonstrate the versatility of catalysis with Earth-abundant metals as pathways involving open- versus closed-shell intermediates can be switched by the energy source.