Groundwater is an essential resource in meeting consumptive demands particularly drinking water worldwide. However, the resource is vulnerable to lithologic and anthropogenic pollution. This study evaluates the vulnerability of South African groundwater resources to fluoride toxicity and the resultant health impacts. Findings based on literature show that the Northern Cape, North West, Limpopo and Western Cape are the hotspots of fluoride toxicity in groundwater as the levels of this contaminant exceed the allowable limit of 1.5 mg/l in these regions. Distribution of this toxicity is spatially different and as evident from the case study of Roundhill landfill vicinity, it is not limited to hotspot areas alone. Karoo fractured rocks that allow easier release of fluoride to groundwater during interaction are the most probable cause of elevated levels in groundwater while improper solid waste disposal and the use of agrochemicals and fertilisers are the anthropogenic sources of this contaminant. Elevated levels of fluoride increase the aetiology of dental and skeletal fluorosis among other health complications and future researches should focus on its removal prior to consumption of groundwater.