A mesoporous CaO-loaded In2O3 material (with Ca/In2O3 ratios ranging from 2.5 to 8.5 at %) has been synthesized and used as resistive gas sensor for the detection of CO2. A nanostructured In2O3 matrix has been obtained by hard template route from the SBA-15 silica template. Additive presence does not distort the lattice of In2O3, which crystallizes in the Ia3 cubic space group. It has been proved by XRD, HRTEM, Raman and XPS measurements that samples contain not only CaO but also CaCO3 in calcite phase as a consequence of CaO carbonation. Pure In2O3 based sensors are low sensitive to CO2, whereas those containing the additive show an important response in the 300–5000 ppm range of gas concentrations. As seen by DRIFTS, the electrical response arises from the interaction between CO32– and CO2, yielding bicarbonates products. The reaction is water-assisted, so that hydration of the sensing material ensures sensor reliability whilst its dehydration would inhibit sensor response. The use of CaCO3 instead of CaO does not cause significant differences in electrical and DRIFTS data, which corroborates the important role played by carbonate species in the sensing mechanism.