The reaction of cobalt(II) pivalate with a spin-labeled Schiff base (HL1) in organic solvents formed trinuclear complex [Co-3(Piv)(2)(L2L22)-L-1]center dot Solv (Solv is Me2CO and/or C7H16 and CH3CN) containing both nitroxide L-1 and the product of its single-electron reduction, nitrone L-2. The formation of [Co-3(Piv)(2)(L2L22)-L-1] was a consequence of an unusual phenomenon, which we called "redox-induced change in the ligand coordination mode". A reduction of L-1 to L-2 led to a change in the set of donor atoms and even in the size of the metallocyde. This phenomenon was also found for mononuclear [(CrL2L2)-L-1] and [(FeL2L2)-L-1]center dot Me2CO.