Ammoniovoltaite, (NH₄)₂Fe²⁺₅Fe³⁺₃Al(SO₄)₁₂(H₂O)₁₈, is a complex hydrated sulphate of the voltaite group that has been recently discovered on the surface of the Severo-Kambalny geothermal field (Kamchatka, Russia). Vibrational spectroscopy has been applied for characterization of the mineral. Both infrared and Raman spectra of ammoniovoltaite are characterized by an abundance of bands, which corresponds to the diversity of structural fragments and variations of their local symmetry. The infrared spectrum of ammoniovoltaite is similar to that of other voltaite-related compounds. The specific feature related to the dominance of the NH₄ group is its ν₄ mode observed at 1432 cm⁻¹ with a shoulder at 1510 cm⁻¹ appearing due to NH₄ disorder. The Raman spectrum of ammoniovoltaite is basically different from that of voltaite by the appearance of an intensive band centered at 3194 cm⁻¹ and attributed to the ν₃ mode of NH₄. The latter can serve as a distinctive feature of ammonium in voltaite-group minerals in resemblance to recently reported results for another NH₄-mineral—tschermigite, where ν₃ of NH₄ occurs at 3163 cm⁻¹. The values calculated from wavenumbers of infrared bands at 3585 cm⁻¹, 3467 cm⁻¹ and 3400 cm⁻¹ for hydrogen bond distances: d(O···H) and d(O···O) correspond to bonding involving H1 and H2 atoms of Fe²⁺X₆ (X = O, OH) octahedra. The infrared bands observed at 3242 cm⁻¹ and 2483 cm⁻¹ are due to stronger hydrogen bonding, that may refer to non-localized H atoms of Al(H₂O)₆ or NH₄.