The geochemical characteristics and the spatial distribution of the fluoride were studied in the soils of Indo-Gangetic plains using multivariate analysis. The fluoride (F) distribution in soil profiles and surface soil (0–15 cm) samples were studied. It was found that total fluoride (TF) in the profiles ranged from 248 to 786 mg kg−1 with a mean of 515.1 mg kg−1 whereas CaCl2 extractable soluble fluoride (FCa) was found to be in the range of 1.68 to 99.1 mg F kg−1 soil. On the other hand, in surface soils, the TF and FCa ranged from 118 to 436 mg kg−1 with a mean of 251.2 mg kg−1 and 1.01 to 5.05 mg kg−1 with a mean of 2.12 mg kg−1, respectively, in the study area. The principal component analysis revealed that the natural weathering of fluoride bearing rock and minerals, various ion-exchange and dissolution processes in the soil, alkalinity, sodium adsorption ratio, calcium (Ca), magnesium (Mg), and clay contents of the soil are responsible for high fluoride occurrence in the area. The fluoride contamination index developed by using these factors could explain more than 76% variance of F contamination due to FCa in soils. The interpolated kriged map of FCa in surface soil indicated a distinct loop of 1.0–2.0, 2.0–3.0, 3.0–4.0, and >4.0 mg kg−1.