The evaluation of the theoretical geothermal potential of identified unexploited hydrothermal reservoirs within the Vicano–Cimino and Sabatini volcanic districts (Latium region, Italy) has been made on the basis of a revised version of the classical volume method. This method is based on the distribution of the partial pressure of CO2 (pCO2) in shallow and deep aquifers to delimit areas of geothermal interest, according to the hypothesis that zones of high CO2 flux, either from soil degassing and dissolved into aquifers, are spatially related to deep hydrothermal reservoirs. On the whole, 664 fluid discharges (cold waters, thermal waters, and bubbling pools) have been collected from shallow and deep aquifers in the Vicano–Cimino Volcanic District and the Sabatini Volcanic District for chemical and isotopic composition, in an area of approximately 2800 km2. From this large hydro-geochemical dataset the pCO2 values have been computed and then processed to obtain a contour map of its spatial distribution by using geostatistical techniques (kriging). The map of pCO2 has been used to draw up the boundaries of potentially exploitable geothermal systems within the two volcanic districts, corresponding to the areas where endogenous CO2 raise up to the surface from the deep hydrothermal reservoirs. The overall estimated potential productivities and theoretical minimum and maximum thermal power of the two volcanic districts are of about 45 × 103 t/h and 3681–5594 MWt, respectively. This makes the Vicano–Cimino Volcanic District and the Sabatini Volcanic District very suitable for both direct and indirect exploitation of the geothermal resources, in view of the target to reduce electricity generation from conventional and poorly sustainable energy sources.