Steady-state photolysis of a series of cobalt(III)-amine complexes, dissolved in neutral air equilibrated aqueous and non-aqueous solvents, with 254 nm penray lamp, leads to the oxygenation of the photoproduced cobalt(II) amine complexes. The study indicates that the photoproduced cobalt(II)-amine complexes upon reaction with molecular oxygen form a superoxo complex that reacts with the starting complex to give a μ-superoxo dinuclear complex. Subsequently the μ-superoxo complex gives the final product, the μ-peroxo dinuclear complex at room temperature. But in aqueous acidic solution the final photoproduct is cobalt(II) aqua complex.