The nevado-filábride complex (NFC) (southern Spain) is well known for its widespread mining and quarrying activities. Serpentinite and metabasite rocks are extracted, processed and traded as building and ornamental stones. Due to the possible presence of natural occurrence of asbestos (NOA) in these rocks, the aim of this paper is to conduct an in-depth characterisation of fibrous minerals. To this aim, seven serpentinite rock samples were collected in four quarries located in the Sierra Nevada and Sierra de los Filabres (South-eastern Spain), which were then analysed by X-ray powder diffraction (XRPD), scanning electron microscopy combined with energy-dispersive spectrometry (SEM/EDS), differential scanning calorimetry (DSC), derivative thermogravimetry (DTG) and X-ray synchrotron microtomography (SR-µCT). It is essential to investigate asbestos minerals from both scientific and legal perspective, especially for public health officials that implement occupational health and safety policies, in order to safeguard the health of workers (e.g. quarry excavations, road yards, civil constructions, building stones).