In order to reveal the enrichment mechanism of groundwater with high fluoride based on the hydrogeological conditions in the Guanzhong basin, the paper analyzed the impact factors of fluoride enrichment in groundwater. The results showed that high fluoride distribution in groundwater has certain hydrogeological characteristics. The fluoride content in groundwater contacts with water temperature, pH and chemical composition. HCO-3and Na + promote the migration and transformation of fluorine-containing minerals to groundwater, but Ca2+ dominate the increase of fluoride content. Factor analysis showed that the water-rock interaction, dissolution of carbonate minerals and Na-Ca ion exchange controls the main hydrochemical process of fluoride enrichment of groundwater in Guanzhong basin. The soluble fluoride in vadose zone migrates downward mainly because of leaching effect.The fluoride enrichment is depend on the role of evaporation and condensation.