The behaviour of ornamental stones in response to environmental changes or interactions is crucial when dealing with the conservation of cultural heritage. Weathering factors affect each rock differently, depending on structure, mineralogy, and extraction and implementation techniques. This work focuses on the Macigno sandstone, a dimension stone often employed in Tuscany over the centuries. A thorough mineralogical (optical microscopy, scanning electron microscopy and X-ray powder diffraction) and petrophysical characterization (i.e. mercury intrusion porosimetry, X-ray computed tomography, hygroscopic adsorption behaviour, ultrasounds, image analysis and capillary uptake) was made of the sandstone type extracted in the area of Greve in Chianti. The lithotype shows mineralogical (i.e. presence of mixed-layer phyllosilicates) and micro-porosimetric features, leading to a high susceptibility to relative humidity variation. Moreover, the influence of swelling minerals is related to weathering due to saline solution. The joint application of petrographic and petrophysical techniques allows an understanding of the characteristic weathering pattern of exfoliation (i.e. detachment of multiple thin stone layers, centimetre scale, that are sub-parallel to the stone surface).