The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe₂O₃/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe₂(SO₄)₃, Fe₂(SO₄)₃·5H₂O, kornelite, coquimbite, Fe(SO₄)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm⁻¹ are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe³⁺ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe²⁺/[Fe²⁺ + Fe³⁺] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.