The carbonate rocks of the Otavi Group (ca. 800 Ma) in the northeastern part of South West Africa/Namibia are known to contain Pb, Zn and Cu sulphide deposits with the mining activities at Tsumeb, Kombat and Berg Aukas being the most prominent. Vanadium mineralisation, associated with karst development, is often associated with the sulphide deposits, but occurrences without a sulphide association are also present. The distribution of Pb, Zn, Cu and V in the dolomite and limestone of the Otavi Mountain Land delineates geochemical regions which coincide with the above mineralisation. This coincidence is also manifest in the type of V mineralisation; where high concentrations of Zn occur in the country rocks, descloizite predominates, whilst mottramite occurs when the Cu values are higher.