Groundwater in South Africa is an essential source of potable water for rural communities, farms and towns. Semi-arid conditions of South Africa, a growing population and surface water resources almost entirely being exploited to their limits, increase the demand for groundwater resources. Therefore, the relation between the geology and geohydrology of South Africa becomes an important tool in locating groundwater resources that can provide sustainable quantities of water for South Africans. A document was therefore compiled, providing valuable geohydrological information on the geological formations of the whole of South Africa. The information was gathered by means of interviews with experienced South African geohydrologists and reviewing of reports and articles of geohydrological studies. The geohydrological characteristics discussed include rock/aquifer parameters and behaviour, aquifer types (primary of secondary), groundwater quality, borehole yields and expected striking depths, and geological target features and the geophysical method used to locate these targets. Due to the fact that 90% of South Africa’s aquifers are classified as secondary aquifer systems, groundwater occurrence within the rocks of South Africa is mainly controlled by secondary fractured systems; therefore, understanding the geology and geological processes (faulting, folding, intrusive dyke/sills and weathering) responsible for their development and how they relate, is important. However, the primary aquifers of South Africa (Coastal Cenozoic Deposits) should not be neglected as these aquifers can produce significant amounts of groundwater. Drilling success rates and possibility of striking higher yielding boreholes can be improved dramatically when an evaluation of the structural geology and geohydrological conditions of an area together with a suitable geophysical method is applied. The ability to locate groundwater has been originally considered (even today) a heavenly gift and can be dated back to the Biblical story of Moses striking the rock to get water: “behold, I will stand there before thee there upon the rocks thou shalt smite the rock and there shall come water out of it” (Exodus 17:6).