O-2 activation at a chromium(II) siloxide complex in propionitrile leads to a chromium(III) complex with an end-on bound superoxide ligand, while the reaction in tetrahydrofuran leads to a side-on peroxo chromium(IV) compound. The superoxide reacts faster with (2,2,6,6-tetramethylpiperidin-1-yl) oxyl hydroxyl amine while the peroxide, unlike the superoxide, proved capable of deformylating aldehydes. The system was found to represent a unique case, where even a switching between the two structures can be achieved via the solvent; its ability to coordinate at the position trans to the O-2 ligand is decisive, as supported by density functional theory studies. Altogether, the results show that subtle changes can determine for an initially formed metal-dioxygen adduct, whether it exists as a superoxide or a peroxide, which thus merits consideration in discussions on mechanisms and possible reaction routes.