We present the first single-crystal Raman spectra of the mineral schafarzikite FeSb2O4 from the Pernek locality of the Slovak Republic. In addition, Raman spectra of the natural mineral apuanite Fe2+Fe43+Sb4O12S, originating from the Apuan Alps in Italy, as well as spectra of synthetic ZnSb2O4 and the arsenite mineral trippkeite (CuAs2O4) are presented for the first time. The spectra of the antimonite minerals are characterized by a strong band in the region 660–680 cm−1 with shoulders on either side, and a band of medium intensity near 300 cm−1. The spectrum of the arsenite mineral is characterized by a medium band near 780 cm−1 with a shoulder on the high wavenumber side and a strong band at 370 cm−1. Mode assignments are proposed based on the spectral comparison between the compounds, symmetry modes of the bands and prior literature. The single-crystal spectra of schafarzikite showed good mode separation, allowing bands to be assigned to the symmetry species of A1g, B1g, B2g, or Eg.