Gas leakage from deep geologic storage formations to the Earth’s surface is one of the main hazards in geological carbon sequestration and storage. Permeable sediment covers together with natural pathways, such as faults and/or fracture systems, are the main factors controlling surface leakages. Therefore, the characterization of natural systems, where large amounts of natural gases are released, can be helpful for understanding the effects of potential gas leaks from carbon dioxide storage systems. In this framework, we propose a combined use of high-resolution geoelectrical investigations (i.e. resistivity tomography and self-potential surveys) for reconstructing shallow buried fracture networks in the caprock and detecting preferential gas migration pathways before it enters the atmosphere. Such methodologies appear to be among the most suitable for the research purposes because of the strong dependence of the electrical properties of water-bearing permeable rock, or unconsolidated materials, on many factors relevant to CO2 storage (i.e. porosity, fracturing, water saturation, etc.). The effectiveness of the suggested geoelectrical approach is tested in an area of natural gas degassing (mainly CH4) located in the active fault zone of the Bolle della Malvizza (Southern Apennines, Italy), which could represent a natural analogue of gas storage sites due to the significant thicknesses (hundreds of meters) of impermeable rock (caprock) that is generally required to prevent carbon dioxide stored at depth from rising to the surface. The obtained 3D geophysical model, validated by the good correlation with geochemical data acquired in the study area and the available geological information, provided a structural and physical characterization of the investigated subsurface volume. Moreover, the time variations of the observed geophysical parameters allowed the identification of possible migration pathways of fluids to the surface.