One possible way of mitigating carbon dioxide (CO₂) emissions from fossil fuel combustion is using carbon dioxide capture and storage (CCS) technology. However, public perception concerning CO₂ storage in the geosphere is generally negative, being particularly motivated by perceived leakage risks. Therefore, a main issue when attempting to gain public acceptance is ensuring provision of appropriate monitoring practices, aimed at providing health, safety and environmental risk assessment, so that potential risks from CO₂ storage are minimized. Naturally occurring CO₂ deposits provide unique natural analogues for evaluating and validating methods used for the detection and monitoring of CO₂ spreading and degassing into the atmosphere. Geological and hydrological structures of the Cheb Basin (NW Bohemia, Czech Republic) represent such a natural analogue for investigating CO₂ leakage and offer a perfect location at which to verify monitoring tools used for direct investigation of processes along preferential migration paths. This shallow basin dating from the Tertiary age is characterized by up to 300 m thick Neogene sediment deposits and several tectonically active faults. The objectives of this paper are to introduce the CO₂ analogues concept to present the Eger Rift as a suitable location for a natural CO₂ analogue site and to demonstrate to what extent such an analogue site should be used (with a case study). The case study presents the results obtained from a joint application of geoelectrical measurements in combination with soil CO₂ concentration and flux determination methods, for the detection and characterization of natural CO₂ releases at gas seeps (as part of a hierarchic monitoring concept). To highlight discharge-controlling structural near surface features was the initial motivation for the application of geoelectrical measurements. Soil-gas concentration and flux measurement techniques are relatively simple to employ and are valuable methods that can be used to monitor seeping CO₂ along preferential pathways. Joint interpretation of both approaches yields a first insight into fluid paths and reveals that the thickness and permeability of site-specific near surface sedimentary deposits have a great influence upon the spatial distribution of the CO₂ degassing pattern at surface level.