Tourmalines, XY 3 Z 6 T 6 O 18 (BO 3 ) 3 V 3 W, are excellent petrogenetic indicators as they capture the signature of the host-rock bulk composition. Raman spectra of tourmalines can be used as fingerprints for species identification and crystal-chemical analysis. While Li-bearing species are directly distinguishable by the shape of the OH-stretching vibrations, the discrimination of Mg- and Fe-dominant species can be hindered by the coexistence of at least two types of octahedrally coordinated R n+ cations. Thirty Li-free tourmaline samples comprising 14 different species were studied by Raman spectroscopy and electron microprobe. All nine Fe 3+ -bearing samples were also analyzed by single-crystal X-ray diffraction and Mossbauer spectroscopy. The Raman scattering analysis shows that Mg-dominant species can be immediately distinguished from Fe-dominant species by the shape of the vibrational modes at ~200–240 cm −1 arising from the YO 6 vibrations. Trivalent Fe can be observed and quantified by shifts of the framework vibrations toward lower wavenumbers. The position of the main ZO 6 vibrational mode (275–375 cm −1 ) can be used to determine the Z Fe 3+ content, while the Y Fe 3+ content can be inferred from the position of the peak at ~315 cm −1 . Fits to the data points indicate that the homovalent substitution of Fe 3+ for Al 3+ leads to a considerably larger downward shift of the ZO 6 vibrational mode than the heterovalent substitution Mg 2+ for Al 3+ . The intensity ratio of the two major YO 6 vibrational modes (200–240 cm −1 ) of the fully characterized Fe 3+ -bearing samples reflects the amount of Y-site Mg and thus can be used to deduce the site-occupancy disorder of Mg over the Y and Z site for tourmaline species with Mg ≤2 apfu. By combining the information from framework and OH-stretching vibrations, Raman spectroscopy alone can be used as a micrometer-scale sensitive non-destructive method for the analysis of tourmaline crystal chemistry including trivalent Fe, which is the major tracer for oxygen fugacity and central for intersite geothermometry.