A study of the crystalline materials on or near the surface of freshly made or "green" superphosphate granules and mature, "set" superphosphate granules was undertaken using X-ray diffraction, X-ray mapping, scanning electron microscopy and electron probe micro analysis techniques. Calcium sulphate (CaSO4), calcium sulphate hemihydrate (CaSO4 1/2H20), and mono calcium phosphate monohydrate (Ca(H2PO4)2H2O), were the only crystalline species present in the "green" superphosphate.In the set superphosphate however, additional compounds were present, namely complex iron and aluminium phosphates Ca(Fe,AI) H(HPO4hF2)2H2O, (Fe)3(H3O)H8 (PO4)6H2O and calcium sulphate dihydrate (CaSO4.2H2O).The complex phosphates tied up the major part of the Fe and Al in the system and were concentrated on or near the surface of the granule. An intimate mixture of CaSO4.2H2O, and CaSO4, along with the above mentioned complex Fe-AI compounds, crystallize close to the surface of the granule and cause the setting of superphosphate that takes place during storage.