Several Jurassic, ophiolite-hosted Cu-Zn VMS deposits occur in Tuscany. They are hosted by tectonic units of oceanic affinity (Ligurian Units), such as the well-known deposits of nearby Liguria. Industrial production was small and definitively ceased in the 1960s. Locally, massive ore (chalcopyrite-bornite-chalcocite) with an exceptionally high grade was found. The Montecatini Val di Cecina mine exploited the largest “bonanza” and, for few decades in the 19th century, became one of the most profitable copper mines in Europe. This study provides an updated review of these deposits. Tuscan Cu-Zn VMSs mostly occur in proximity of the contact between the serpentinite-gabbro basement and the overlying basalts. Chalcopyrite-pyrite stockworks occur in serpentinite-gabbro cut by dolerite dykes, while the largest massive sulphide bodies are hosted by polymictic-monomictic breccias at the base of pillow basalts. Early chalcopyrite ores were mechanically–chemically reworked and upgraded to bornite-rich nodular ore embedded in a chlorite, calcic amphibole, Fe-rich serpentine, quartz, andradite, ilvaite, and xonotlite assemblage. This bornite-rich ore contains substantial amount of sphalerite and pyrite and ubiquitous grains of clausthalite, hessite, tellurium, and gold. They represent a prime example of the sub-seafloor portion of a hybrid mafic-ultramafic oceanic hydrothermal system formed in an OCC along the slow spreading ridge of the Jurassic Piedmont-Ligurian Ocean. The peculiar mineralogical–textural character of the bornite-rich ore was driven by an interface coupled dissolution–precipitation process mediated by fluids.