CO2 storage in the subsurface is becoming more and more attractive as a means to reduce CO2 emissions to the atmosphere and hence minimize human-induced global warming. The ability to monitor and verify these CO2 storage reservoirs is a key element for further implementation of other storage sites. Since the current sites fortunately do not appear to "leak" CO2, it is difficult to test the most suitable monitoring techniques for their ability to detect CO2 migration pathways. In this study different monitoring methods have been evaluated at a site in the Latera caldera (central Italy) where natural, thermo-metamorphically produced CO2 finds its way to the surface. The aim of the study is to identify which monitoring methods can detect the migrating CO2 and to gain understanding of the preferential migration pathways of the CO2. Different geophysical monitoring techniques have been deployed at a small, 200×500 m study area located in the centre of the caldera: 2D reflection seismics (testing different sources), 2D refraction seismics, multi-channel analysis of surface wave (MASW), ground penetrating radar (GPR), micro-gravity, magnetometer, self-potential (SP), 2D and 3D geo-electrical measurements and electro-magnetic (EM31 and EM34) measurements. Furthermore CO2 flux measurements were performed in a dense grid over the study area, and a limited number of soil gas samples collected along two profiles, to "ground-truth" the geophysical results. In general a good correlation has been observed between the different methods and the presence of CO2. Geophysical responses, especially those of the reflection seismic and magnetometer data, change markedly from one side of the proposed main fault to the other, probably linked to a sharp geological boundary. The observed fractures on the seismic data seem to correspond with the preferred migration pathways of the CO2. The GPR and resistivity measurements detect strong variations in conductivity induced by the presence of the CO2 up to about 2 and 20 m depth, respectively, as supported by the soil gas and flux measurements. © 2009 Elsevier Ltd. All rights reserved.