We have carried out optical microscopy, X-ray diffraction (XRD) and scanning and transmission electron microscopy (SEM and TEM) studies of phyllosilicates from black slates of very low to low-grade metamorphism. Such slates belong to a Middle/Late Devonian basin and an Early Carboniferous basin associated with the Porto–Tomar–Ferreira do Alentejo strike-slip shear zone (Ossa-Morena Zone, Portuguese Iberian Variscan Massif). These black slates are imbricated in an Upper Proterozoic substratum of higher metamorphic grade. Kübler Index values of white micas and mineral assemblages deduced from the XRD, SEM and TEM data (muscovite, chlorite and pyrophyllite) indicate high anchizonal and epizonal metamorphic conditions for slates from these basins. The b parameter and the phengitic contents of mica suggest the occurrence of low pressures (1–2 kbar) related to an extensional geotectonic setting. The dense fracture network shown by SEM images and the high density of crystal defects revealed by the TEM study in the eastern basin, adjacent to faults produced by shearing, suggest that their epizonal phyllosilicates were more affected during deformation than those belonging to the western basin, favouring the development of a retrograde association (siderite, kaolin group minerals and Al-smectite) on the epizonal paragenesis. Microcavities formed along phyllosilicate cleavage acted as channels for fluid transport favouring alteration under low-temperature conditions.