There is a growing attention in valuable trace elements (TEs) in coal and coal combustionproducts as they can potentially be future resources of valuable TEs. Therefore, understanding the mode of occurrences of valuable TEs in coal has several advantages for their economical and industrial extractions. Since there is limited information on the affinity of valuable TEs in the structure of African coals, this study explores correlations between conventional coal properties and concentration of vanadium, yttrium, gallium and lithium as valuable TEs for a wide range of African coal samples (139 samples) from South Africa, Botswana, Egypt, Tanzania, Nigeria and Zambia by statistical methods. Statistical assessments indicated that the concentrations of Y, V, Li and Ga for these countries are higher than their value in the world coal (on average). The outcomes of assessments showed that the Li, Ga and V are associated with the mineral matter fraction (inorganic affinity) of the coal where they have significant positive correlations with ash and Al (as a major element) and potentially clay minerals are their main bearing minerals. However, statistical explorations suggested that Y may have both the organic and inorganic occurrences in the African coal samples