We report lithium (Li) isotopic measurements in seawater-derived waters that were discharged from geothermal wells, thermal springs, and submarine springs located in volcanic island arc areas in Guadeloupe (the Bouillante geothermal field) and Martinique (Lamentin plain and the Diamant areas). While Li isotopic signatures of the geothermal fluids collected from deep reservoirs were found to be homogeneous for a given site, the δ7Li signatures for each of these reservoirs were significantly different. The first low temperature (25-250°C) experiments of Li isotope exchange during seawater/basalt interaction confirmed that Li isotopic exchange is strongly temperature dependent, as previously inferred from natural studies. Li isotopic fractionation ranged from +19.4‰ (Δ solution - solid) at 25°C to +6.7‰ at 250°C. These experiments demonstrated the importance of Li isotopic fractionation during the formation of Li-bearing secondary minerals and allowed us to determine the following empirical relationship between isotopic fractionation and temperature: Δ solution – solid = 7847 / T – 8.093. Application of experimental results and literature data to the Bouillante area suggested that geothermal water was in equilibrium at 250-260°C. It likely has a deep and large reservoir located in the upper sheeted dike complex of the oceanic crust, just below the transition zone between andesite volcanic flows and the basaltic dikes. The upper dike section, from which Li is extracted by hydrothermal fluids, was characterized by light Li isotopic values in the rocks, indicating retention of 6Li by the altered rocks. For the Lamentin and Diamant areas, the geothermal fluids appeared to be in equilibrium with reservoir volcano-sedimentary rocks at 90-120°C and 180°C, respectively. Further evidence for this argument is provided by the fact that only the Na/Li thermometric relationship determined for sedimentary basins yielded temperature values in agreement with those measured or estimated for the reservoir fluids. This suggests the importance of a sedimentary signature in these reservoir rocks. Altogether, this study highlights that the use of Li isotopic systematics is a powerful tool for characterizing the origin of geothermal waters as well as the nature of their reservoir rocks.