Fresh water availability has recently become a serious concern in the Italian Apennines, as various activities rely on a predictable supply. Along the ridge between Scansano and Magliano in Toscana, in southern Tuscany, the situation is further complicated by contamination of the nearby alluvial aquifers. Aquifers locally consist of thin fractured reservoirs, generally within low-permeability formations, and it can be difficult to plan the exploitation of resources based on conventional techniques. An integrated study based on geological data investigated the link between tectonics and groundwater circulation, to better define the hydrological model. After the regional identification of fault and fracture patterns, a major structure was investigated in detail to accurately map its spatial position and to understand the geometry and properties of the associated aquifer and assess its exploitation potential. The subsurface around the fault zone was clearly imaged using ground probing radar, two-dimensional and three-dimensional resistivity tomography, and three-dimensional shallow seismic surveys. The vertical and horizontal contacts between the different geological units of the Ligurian and Tuscan series were resolved with a high degree of spatial accuracy. Three-dimensional high-resolution geophysical imaging proved to be a very effective means of characterising small-scale fractured reservoirs.