Mixed-valence trinuclear iron propionates [Fe2IIIFeIIO(C2H5CO2)6(py)3]npy, where n=0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Mössbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. © 1994 J.C. Baltzer AG, Science Publishers.