The chrysotile fibres toxicity appears correlated to the redox activity of iron present in the chrysotile structure. In fact the generation of reactive oxygen species and other radicals appears catalyzed by iron ions and closely related to Fe ions organization in specific crystallographic sites having a capability to activate free radical generation. The Fe substitution to Mg and/or Si in the chrysotile structure appears important for asbestos health hazard investigation. Infrared and Raman spectroscopic analyses have been utilized to investigate Mg and/or Si ions replacement by Fe ions in chrysotile structure as a function of the Fe doping extent. Geoinspired synthetic chrysotile at different Fe doping extents has been obtained as unique phase by hydrothermal reaction in the presence or not of metallic Fe in the synthetic environment. The results highlight that Fe can replace both Mg and Si, differently modifying the chrysotile structure as a function of the Fe doping extent and the Fe doping process. The contemporary iron substitution into the octahedral and tetrahedral sheets reveals an appreciable increase of the dehydroxylation temperature which occurs at higher temperature than for iron-free sample. The results highlight the role of Fe substitution in the asbestos structure influencing the health hazard of biological systems.