Vanadium(V) can be found in natural waters in the form of V(IV) and V(V) species, which have different biological properties and toxicity. The purpose of this study was to determine the concentrations of total V and V(V) in groundwater from the area of Mt. Etna and to assess the estimated daily intake (EDI) of V(V) of adults and children through drinking water. Water was sampled monthly at 21 sites in 2011. Total vanadium was determined by inductively coupled plasma-mass spectrometry (ICP-MS) and speciation by ion chromatography-ICP-MS (IC-ICP-MS). The concentration of V(V) species ranged from 62.8 to 98.9% of total V, with significantly higher concentrations in samples from the S/SW slope of Mt. Etna. The annual mean concentrations of total V exceeded the Italian legal limit of 140 μg/L at four sites on the S/SW slope. In the absence of thresholds for V(V) intake, only the Environmental Protection Agency (EPA) has calculated a reference dose. Children's EDI of V(V) at the sites with the higher V concentrations exceeded EPA thresholds (9 μg/kg/day). In particular, we found in Camporotondo, Mascalucia, Ragalna and San Pietro Clarenza sites children's EDIs of 11, 9.3, 11 and 9.9, respectively. The EDI of V(V) was significantly higher than the literature range (0.09–0.34 μg/kg/day).