Abstract We report here the infrared and Raman spectra of [Re(CN)5NO]3− complex as guest diluted in the KCl crystal lattice. According to the chemical analysis, the anion concentration in the KCl host matrix is in excess of 2% (in mole). The solid state Raman spectrum of this complex is reported for the first time. The information obtained from the relative intensities of infrared and Raman bands affords a reexamination of vibration mode assignments. The observed bands splitting may be explained by the interactions of the guest complex with the host lattice, including the ways in which the K+ vacancies are distributed around [Re(CN)5NO]3− to achieve lattice charge neutrality.