Abstract This chapter deals with the use of vibrational spectroscopies, i.e . FTIR and Raman, for the study of asbestos minerals. Both techniques have been applied extensively for studies on amphiboles and layer silicates. According to factor group analysis, FTIR and Raman spectra show the same number of bands in the OH-stretching region (4000–3000 cm −1 ) whereas in the lower frequency range (<1200 cm −1 ) the spectra are much more complex and significantly different. In this region, vibrations due to the tetrahedral double-chain, met al-oxygen modes and OH librations overlap, thus making the assignment of the observed bands difficult. FTIR spectroscopy has been used extensively in recent decades for crystal-chemical studies and as a tool for characterizing short-range and long-range arrangements in amphiboles and layer silicates. A large corpus of data, summarized and discussed in the text, shows that Raman spectroscopy in the low-frequency region is valuable as an identification tool for the regulated asbestos silicates; for this reason, Raman microscopy, also thanks to its intrinsic higher spatial resolution compared to FTIR, has been used extensively to study fibrous minerals in environmental and biomedical applications. Selected examples of these applications are described.