Volcanic risk at Vesuvius is one of the highest in the world due to the ~670,000 inhabitants living in the Red Zone, the area exposed to both pyroclastic flows and tephra fallout, to be evacuated before renewal of any eruptive activity. The national emergency plan for Vesuvius builds its risk zonation on a scenario similar to the last sub-Plinian eruption, which occurred in 1631. This study aims at providing new insights on the geometry of the caldera associated with this historical eruption. The impact of past Vesuvius eruptions on present-day soil CO2 concentration has been investigated by means of an extended geochemical survey carried out for identifying the circulation pathways of hydrothermal fluids inside the volcano. We performed 4018 soil CO2 concentration measurements over the whole Somma-Vesuvius volcanic complex, covering an area of 50 km2. Besides relatively low values, the results show a significant spatial CO2 concentration heterogeneity over Somma-Vesuvius ranging from the atmospheric value (~400 ppm) up to ~24,140 ppm. The summit of Vesuvius shows an area with anomalous CO2 concentrations well matching the crater rim of the 1906 eruption. Along the cone flanks, secondary CO2 anomalies highlight a roughly circular preferential pathway detected along 8 radial profiles at distances between ~840 m and ~1150 m from the bottom of the present-day crater resulting from the last eruption in 1944. In depth review of the available literature highlights an agreement between this circle-like shaped anomaly and the 1631 sub-Plinian eruption caldera boundary. Indeed, based on the historical chronicles the depression produced by the 1631 eruption had a diameter of 1686 m, whereas the CO2 circular anomaly indicates a diameter of 1956 m. Finally, the results were compared with a 3-D density model obtained from a recent gravity survey that corroborates both the literature and the CO2 data in terms of potential buried structure at the base of the Vesuvius cone.