a b s t r a c tNatural analogs offer a valuable opportunity to investigate the long-term impacts associated with the potential leakage in geological storage of CO 2 .Degassing of CO 2 and radon isotopes ( 222 Rn-220 Rn) from soil, gas vents and thermal water discharges was investigated in the natural analog of Campo de Calatrava Volcanic Field (CCVF; Central Spain) to determine the CO 2 -Rn relationships and to assess the role of CO 2 as carrier gas for radon. Furthermore, radon measurements to discriminate between shallow and deep gas sources were evaluated under the perspective of their applicability in monitoring programs of carbon storage projects.CO 2 flux as high as 5000 g m −2 d −1 and 222 Rn activities up to 430 kBq m −3 were measured; 220 Rn activities were one order of magnitude lower than those of 222 Rn. The 222 Rn/ 220 Rn ratios were used to constrain the source of the Campo de Calatrava soil gases since a positive correlation between radon isotopic ratios and CO 2 fluxes was observed. Thus, in agreement with previous studies, our results indicate a deep mantle-related origin of CO 2 for both free and soil gases, suggesting that carbon dioxide is an efficient carrier for Rn. Furthermore, it was ascertained that the increase of 222 Rn in the soil gases was likely produced by two main processes: (i) direct transport by a carrier gas, i.e., CO 2 and (ii) generation at shallow level due to the presence of relatively high concentrations of dissolved U and Ra in the thermal aquifer of Campo de Calatrava.The diffuse CO 2 soil flux and radon isotopic surveys carried out in the Campo de Calatrava Volcanic Fields can also be applicable to geochemical monitoring programs in CCS (Carbon Capture and Storage) areas as these parameters are useful to: (i) constrain CO 2 leakages once detected and (ii) monitor both the evolution of the leakages and the effectiveness of subsequent remediation activities. These measurements can also conveniently be used to detect diffuse leakages.