The allophane studied occurs in the weathered zones of the barite-sulphide-bearing dolomitic levels, interbedded in the barite ore deposits of Vide de Alba and San Bias (Province of Zamora). These ore deposits are interstratified in the Silurian-Devonian sulphide bearing volcano sedimentary materials of the Alcañices Synform. The allophanic samples have been studied by polarizing microscopy, SEM, XRD, DTA, TG, IRS, EMA and chemical analyses, the last after dissolving the samples by acid (HF + HNO3 + 3HCl + H3BO3) and alkaline digestion (0·5 m NaOH). It is suggested that allophane originates from the reaction of acid solutions released during the weathering of sulphides with acid volcanoclastic rocks. Silica-alumina gels were deposited in holes formed during earlier dissolution of the dolomite associated with the barite ores. Later processes of desilication partially transform allophane to gibbsite.