Reaction of 4,4,4′,4′-tetramethyl-2,2′-bisoxazoline (L) with RhCl 3 in methanol followed by addition of excess NaClO 4 yields cis-[RhL 2 Cl 2 ]ClO 4 (1). Complex 1 hydrolyses to yield the mixed ligand Rh(III) complex trans-[RhL(L′H)Cl 2 ]ClO 4 ·2H 2 O (2), where L′H is 2-amino-2-methyl-1-propanol (H: dissociable alcoholic proton). The X-ray crystal structures of 1 and 2 have been determined. The aminoalcohol L′H binds the metal in 2 in bidentate mode through the N and the O ends. The 1 H NMR of 2 in CD 3 CN shows that the alcoholic proton dissociates in solution. DFT calculations at the B3LYP/LanL2DZ level reveal that the dissociation of the alcoholic proton in 2 is highly exothermic and accompanied with elimination of a chloride ion from the metal coordination sphere giving rise to a square pyramidal five-coordinate Rh(III) species. The relevant pK a value has been determined in acetonitrile from solution conductance as 8.98 (±0.27). Both the complexes 1 and 2 display an irreversible Rh(III/I) couple in cyclic voltammetry in acetonitrile at a glassy carbon electrode around −0.35V versus NHE.