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The 57Fe Mössbauer spectra of three isomorphous compounds of the type Fe4[MB(CN)6]3 · xH2O, where MB is Fe, Ru or Os, have been measured in the temperature range between −178 and 25°C. The spectral pattern of the ruthenium and osmium compounds is very similar to that of selectively enriched 57Fe4[Fe(CN)6]3 · xH2O. The temperature dependence of the isomer shift and quadrupole splitting is interpreted in terms of lattice dynamics. The X‐ray photoelectron spectra also support the conclusions drawn from the Mössbauer study.