In this paper, we use carbon isotopes in the dissolved load of rivers from the Lesser Antilles volcanic arc (Guadeloupe, Martinique and Dominica islands) to constrain the source of the carbon dioxide (CO2) involved in the neutralization reactions during water–rock interactions. The δ13C data span a large range of variations, from –19‰ to –5 · 2‰ for DIC (dissolved inorganic carbon) concentrations ranging from 11 μM to 2000 μM. Coupled with major element concentrations, carbon isotopic ratios are interpreted as reflecting a mixture of magmatic CO2 (enriched in heavy carbon (δ13C ≈ –3 · 5‰) and biogenic CO2 produced in soils (enriched in light carbon (δ13C < –17‰)). Carbon isotopes show that, at the regional scale, 23 to 40% of CO2 consumed by weathering reactions is of magmatic origin and is transferred to the river system through aquifers under various thermal regimes. These numbers remain first-order estimates as the major uncertainty in using carbon isotopes as a source tracer is that carbon isotopes can be fractionated by a number of processes, including soil and river degassing. Chemical weathering is clearly, at least, partly controlled by the input of magmatic CO2, either under hydrothermal (hot) or surficial (cold) weathering regimes.