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In order to use lithium isotopes as tracers of silicate weathering, it is of primary importance to determine the processes responsible for Li isotope fractionation and to constrain the isotope fractionation factors caused by each process as a function of environmental parameters (e.g. temperature, pH). The aim of this study is to assess Li isotope fractionation during the dissolution of basalt and particularly during leaching of Li into solution by diffusion or ion exchange. To this end, we performed dissolution experiments on a Li-enriched synthetic basaltic glass at low ratios of mineral surface area/volume of solution (S/V), over short timescales, at various temperatures (50 and 90°C) and pH (3, 7, and 10). Analyses of the Li isotope composition of the resulting solutions show that the leachates are enriched in 6 Li (d 7 Li = +4.9 to +10.5&) compared to the fresh basaltic glass (d 7 Li = +10.3 ± 0.4&). The d 7 Li value of the leachate is lower during the early stages of the leaching process, increasing to values close to the fresh basaltic glass as leaching progresses. These low d 7 Li values can be explained in terms of diffusion-driven isotope fractionation. In order to quantify the fractionation caused by diffusion, we have developed a model that couples Li diffusion with dissolution of the glassy silicate network. This model calculates the ratio of the diffusion coefficients of both isotopes (a = D 7 /D 6 ), as well as its dependence on temperature, pH, and S/V. a is mainly dependent on temperature, which can be explained by a small difference in activation energy (0.10 ± 0.02 kJ/mol) between 6 Li + and 7 Li + . This temperature dependence reveals that Li isotope fractionation during diffusion is low at low temperatures (T < 20°C), but can be significant at high temperatures. However, concerning hydrothermal fluids (T > 120°C), the dissolution rate of basaltic glass is also high and masks the effects of diffusion. These results indicate that the high d 7 Li values of river waters, in particular in basaltic catchments, and the fractionated values of hydrothermal fluids are mainly controlled by precipitation of secondary phases.