The photolytic activation of palladium(II) and platinum(II) complexes [M(BPI)(R)] (R = alkyl, aryl) featuring the 1,3-bis(2-pyridylimino)isoindole (BPI) ligand has been investigated in various solvents. In the absence of oxygen, the formation of chloro complexes [M(BPI)Cl] is observed in chlorinated solvents, most likely due to the photolytic degradation of the solvent and formation of HCl. The reactivity of the complexes toward oxygen has been studied both experimentally and computationally. Excitation by UV irradiation (365 nm) of the metal complexes [Pt(BPI)Me] and [Pd(BPI)Me] leads to distortion of the square-planar coordination geometry in the excited triplet state and a change in the electronic structure of the complexes that allows the interaction with oxygen. TD-DFT computational studies suggest that, in the case of palladium, the Pd(III) superoxide intermediate [Pd(BPI)(κ1-O2)Me] is formed and, in the case of platinum, the Pt(IV) peroxide intermediate [Pt(BPI)(κ2-O2)Me]. For alkyl complexes where metal–carbon bonds are sufficiently weak, the photoactivation leads to the insertion of oxygen into the metal–carbon bond to generate alkylperoxo complexes: for example [Pd(BPI)OOMe], which has been isolated and structurally characterized. For stronger M–C(aryl) bonds, the reaction of [Pt(BPI)Ph] with O2 and light results in a Pt(IV) complex, tentatively assigned as the peroxo complex [Pt(BPI)(κ2-O2)Ph], which in chlorinated solvents reacts further to give [Pt(BPI)Cl2Ph], which has been isolated and characterized by scXRD. In addition to the facilitation of oxygen insertion reactions, UV irradiation can also affect the reactivity of other components in the reaction mixture, such as the solvent or other reaction products, which can result in further reactions. Labeling studies using [Pt(BPI)(CD3)] in chloroform have shown that photolytic reactions with oxygen involve degradation of the solvent.