The influence of the solvent on the structure and IR spectrum of the [Fe(CN)(5)NO](2-) ion is investigated by using gradient corrected density functional theory. IR spectra are also measured on different solvents and the results obtained are compared with the predicted ones. We have treated the solvent effects with a continuum model, based on the Onsager’s reaction field approach; in order to mimic strong specific interactions, calculations were also performed on the complex protonated at the cyanide trans to the nitrosyl group. The reaction field calculations predict only qualitatively the most important observed bends, e.g., the shifts in the nitrosyl stretching wavenumber, but fail in accounting quantitatively for the differences between the spectra in water and acetonitrile. The possible role of specific interactions is consistently accounted for by interpreting the experimental shifts of the NO stretching wavenumber nu(NO), as well as the visible absorption energies, when changing the Lewis acidity of the solvent, as measured by the Gutmann’s acceptor number. Ligand population analysis was performed to relate the solvent effects with the sigma donor and pi acceptor behavior of cyanide and nitrosyl ligands. The significance of nu(NO) shifts as a result of changes in the medium is discussed in view of the physiological relevance of transition-metal nitrosyl chemistry.