The Xingtai piedmont plain in Hebei Province is a representative area in northern China where endemic fluorosis is serious and shallow high-F ground water is distributed. In this paper, the area is selected as a typical study area, and on the basis of large amounts of field work and the experiments, through groundwater geochemical modelling and by applying the theory and method of the coupled model of hydrodynamic transport and chemical reactions in a multicomponent system, the author performed numerical modelling of the geochemical behaviour of fluoride in a shallow groundwater system, quantitatively studied the hydrodynamic transport and chemical reaction of fluorine migration, transformation and concentration in a water-heterogeneous unsaturated soil system under the conditions of meteoric water infiltration and quantitatively determined the speciation of fluorine and the saturation state and dissolution/precipitation trend of various solid precipitates in shallow high-F groundwater, thus deepening the understanding of the geochemical behavious of fluorine in shallow groundwater and revealing the essence of some environmental problems at a higher level.