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This paper deals with the importance of chemical analyses in characterising prehistoric pottery fabrics. Two three-year projects focussed on the minero-petrographic and SEM/EDS analyses of the oldest pottery from south-east Europe (ca. 6000 cal BC). Whereas in the Impressed Ware culture of the Adriatic region, optical microscopy was sufficient to identify provenance, the more uniform geological background of the central Balkans required chemical analyses to be able to differentiate between different raw materials. Multiple bulk analyses of each sherd were obtained to gauge the variability in composition within each vessel. The limiting factor in determining provenance in this area appears to be the similarity of clay sources, not the inhomogeneity of the coarse pottery. This is shown here using results from four of the sites, including three where petrographic analyses could not establish provenance.