This study reviewed groundwater fluoride and the associated human health risks in Ghana. The physical and chemical properties of fluorine that make it soluble in the soil and aquifer materials were carefully reviewed. The pathways through which fluoride gets into groundwater were also reviewed. Fluoride concentrations in groundwater can be as high as 67 mg/L. Its natural concentration in water depends largely on the nature of the geologic formations; fluoride-bearing minerals, anion exchange capacity of aquifer materials (OH- for F-), pH, temperature and residence time of waters within a particular formation. High F- concentrations in groundwater are due to geogenic and anthropogenic sources. The fluorosis endemic parts of Ghana are only restricted to northern Ghana, where elevated groundwater fluoride concentrations (0.05-13.29 mg/L) in the North East Region, Northern Region, Upper East Region, and surrounding communities have been reported. The elevated groundwater fluoride concentrations are as a result of intense water-rock interaction, ion exchange reactions, and mineral dissolution from the Bongo Granitoids and Voltaian sediments. Children in the fluorosis endemic parts of Ghana are exposed to the intake of more fluoridated water than the other age groups and thus, children have higher non-carcinogenic risks. Although, almost all the age groups show evidence of dental fluorosis, children are the hypersensitive population. It is recommended that sustainable defluoridation methods such as adsorption, precipitation, membrane separation and ion exchange techniques be employed to curtail the menace of dental fluorosis.