Arsenic (As) contamination in drinking water and agricultural soil has been studied and the adverse effects are observed in both crop and human health. The contamination of groundwater by naturally occurring arsenic in Africa has received little attention compared to the widespread arsenic endemic areas in Asia. The availability, quantity, and quality of groundwater are determined by geological conditions in African regions. Arsenic contamination is prevalent in mining intensive regions of Africa. Weathering of aquifer matrix and anthropogenic activities are also accountable for the release of heavy metals into groundwater in semi-arid coastal aquifers of South Africa as well as regions of the Rift Valley in East Africa. In Northern Egyptian delta lake region, agricultural sites have been associated with pesticides containing arsenic and industrial wastewater flows. Consequently, arsenic leaches into the groundwater which is the main source of drinking and irrigation water. The arsenic enters the entire food supply chain, consequently affecting the human health negatively. In most African countries, levels of arsenic in water are usually above the stipulated standard by the World Health Organisation (WHO) of 0.01 mg/l. Vegetables grown in contaminated soils could accumulate arsenic in their edible parts and elevate dietary arsenic exposure to humans and animals. Research shows elevated arsenic levels in irrigated vegetables in Burkina Faso, Ethiopia and Zimbabwe. Health complications have also increased through the consumption of contaminated water and food in Western and East African countries. Studies on arsenic occurrence, and mobilization in African water systems, as well as related health effects are limited, due to the lack of awareness. This review paper examines arsenic groundwater contamination, its effect on food systems of Sub-Sahara Africa and the associated risks.