A cement asbestos compound (CAC) sample was detoxified by a treatment train based on a dark fermentation (DF) process followed by a hydrothermal phase, which led to the complete degradation of the chrysotile fibers. During the biological pretreatment, the glucose was converted in biogas rich in H-2 and volatile fatty acids (VFA). The latter caused the dissolution of all the Ca-based compounds and the solubilisation of 50% brucite-like layers of chrysotile fibers contained in the CAC suspended in the bioreactor (5 g/L). XRD analysis of the solids contained in the effluents of the DF process highlighted the disappearance of the chrysotile fiber peaks. However, a complete destruction of all the asbestos fibers is hard to prove and a hydrothermal treatment was carried out to dissolve the "brucite" layers still present in solution. Due to the presence of the VFA produced during the DF, a complete destruction of chrysotile fibers was achieved by a 24 h hydrothermal process performed with a [H2SO4]/[CAC] ratio 50% lower than that adopted in a previous finding. Consequently, the DF pre-treatment can contribute to lower the H2SO4 and the energy consumption of a CAC hydrothermal treatment, due to the production of VFA and H-2.