a b s t r a c tThe thermo-mineral fluids discharges of Montecatini Terme (Northern Apennines, Tuscany, Italy) have been exploited since the Roman times and despite the fact that this thermal complex is one of the biggest in Europe, the most recent geochemical investigations were published almost 40 years ago. To fill this gap, in this paper a detailed geochemical and isotopic investigation on the main thermal springs and wells from the Montecatini thermal system (MTS) is presented.The chemical and isotopic features of the Montecatini waters suggested that they are mainly controlled by water-rock interaction processes between meteoric water, permeating at depth from the surrounding reliefs (up to 800 m a.s.l.), and the Triassic evaporites (Burano Formation) belonging to the Tuscan sedimentary series. The local stratigraphic and tectonic framework favors an efficient recharge of the hydrothermal reservoir by the meteoric precipitation from a large catchment area and this aspect plays a fundamental role for the longevity of the Montecatini thermal spas, notwithstanding the huge amount of thermal water exploited. The C-TDIC values were lower than those expected for a mantle/thermometamorphic CO 2 source. This can be explained by: (i) isotopic fractionation occurring during calcite precipitation and/or (ii) mixing with biogenically derived gases, occurring at relatively shallow depth.