The main goal of the monitoring stage of Carbon Capture and Storage (CCS) is to obtain an accurate estimation of the subsurface CO2 accumulation and to detect any possible leakage. Laboratory experiments are necessary to investigate the small scale processes governing the CO2–brine–rock interaction. They also provide a means to calibrate the results coming from field scale geophysical methods. In this work we set up an experimental system which is able to perform Electrical Resistivity Tomography (ERT) measurements on centimeter-scale rock samples at various P–T conditions. We present the results of two new experiments related to CO2 monitoring, performed on a cylindrical (4×8cm) Fontainebleau rock sample. In the first one, we have quantified the CO2 saturation at different volume fractions, representing zones from a deep saline aquifer with varying degrees of saturation. In the second one, we have monitored and quantified the effect of CO2 dissolution in the brine at a pressure of 40bar during eight days, emulating the invasion of CO2 into a shallow aquifer. Results highlight the importance of accounting for the contribution of surface conductivity in highly CO2-saturated regions, even in clay-free rocks, and also for brine conductivity variation due to CO2 dissolution. Ignoring any of these effects will end up in a CO2 saturation underestimation. We present a modified CO2 saturation equation to account for these two influences.