The groundwater is the only source of drinking water in the Jaisalmer district of Rajasthan, India. The study area is a part of the Thar Desert. It has low and scattered population and no industries; hence, the possibility of anthropogenic input of fluoride is almost negligible. Thus, the enrichment of fluoride is only possible due to geochemical processes taking place in the groundwater of the region. A total of 100 groundwater samples, 34 samples from Jaisalmer and 66 samples from the Pokharan administrative blocks, were collected. It was observed that the concentration of fluoride ranged from 0.08 mg/l to 4.56 mg/l in the groundwater of Jaisalmer and from 0.56 mg/l to 6.60 mg/l in the samples of the Pokharan block. The alkaline condition (average pH, 7.7 ± 0.22 and 8.01 ± 0.25 in Jaisalmer and the Pokharan administrative block, respectively) in the region favours fluorite dissolution. Ion exchange, dissolution of calcite, semi-arid climate, alkaline conditions and weathering are responsible for fluoride enrichment in the groundwater of the study area. Copyright © 2012 John Wiley & Sons, Ltd.