Geophysical methods are essential for exploration and monitoring of subsurface formations, e.g. in carbon dioxide sequestration or enhanced geothermal energy. One of the keys to their successful application is the knowledge of how the measured physical quantities are related to the desired reservoir parameters. The work presented in this thesis shows that the presence of carbon dioxide (CO2) in pore space gives rise to multiple processes all of which contribute to the electrical rock conductivity variation. Basically, three mechanisms take place: (1) CO2 partially replaces the pore water, which is equivalent to a decrease in water saturation. (2) CO2 chemically interacts with the pore water by dissolution and dissociation. These processes change both the chemical composition and the pH of the pore filling fluid. (3) The low-pH environment can give rise to mineral dissolution and/or precipitation processes and changes the properties of the grain-water interface. Investigations on the pore water phase show that the reactive nature of CO2 in all physical states significantly acts on the electrical conductivity of saline pore waters. The physico-chemical interaction appears in different manifestations depending mainly on the pore water composition (salinity, ion types) but also on both temperature and pressure. The complex behaviour includes a low- and a high-salinity regime originating from the conductivity increasing effect of CO2 dissociation, which is opposed by the conductivity decreasing effect of reduced ion activity caused by the enhanced mutual impediment of all solutes. These results are fundamental since the properties of the water phase significantly act on all conduction mechanisms in porous media. In order to predict the variation of pore water conductivity, both a semi-analytical formulation and an empirical relationship for correcting the pore water conductivity, which depends on salinity, pressure and temperature, are derived. The central part of the laboratory experiments covers the spectral complex conductivity of water-bearing sand during exposure to and flow-through by CO2 at pressures up to 30MPa and temperatures up to 80°C. It is shown that the impact of CO2 on the real part of conductivity of a clean quartz sand is dominated by the low- and high-salinity regime of the pore water. The obtained data further show that chemical interaction causes a reduction of interface conductivity, which could be related to the low pH in the acidic environment. This effect is described by a correction term, which is a constant value as a first approximation. When the impact of CO2 is taken into account, a correct reconstruction of fluid saturation from electrical measurements is possible. In addition, changes of the inner surface area, which are related to mineral dissolution or precipitation processes, can be quantified. Both the knowledge gained from the laboratory experiments and a new workflow for the description and incorporation of geological geometry models enable realistic finite element simulations. Those were conducted for three different electromagnetic methods applied in the geological scenario of a fictitious carbon dioxide sequestration site. The results show that electromagnetic methods can play an important role in monitoring CO2 sequestration. Compared to other geophysical methods, electromagnetic techniques are generally very sensitive to pore fluids. The proper configuration of sources and receivers for a suitable electromagnetic method that generates the appropriate current systems is essential. Its reactive nature causes CO2 to interact with a water-bearing porous rock in a much more complex manner than non-reactive gases. Without knowledge of the specific interactions between CO2 and rock, a determination of saturation and, consequently, a successful monitoring are possible only to a limited extend. The presented work provides fundamental laboratory investigations for the understanding of the electrical properties of rocks when the reactive gas CO2 enters the rock-water system. All laboratory results are put in the context of potential monitoring applications. The transfer from petrophysical investigations to the planning of an operational monitoring design by means of close-to-reality 3D FE simulations is accomplished.