Handheld portable energy-dispersive X-ray fluorescence (pXRF) spectrometry is used for non-destructive chemical characterization of archaeological ceramics. Portable XRF can provide adequate analytical sensitivity to discriminate geochemically distinct ceramic pastes, and to identify compositional clusters that correlate with data patterns acquired by NAA or other high sensitivity techniques. However, successful non-destructive analysis of unprepared inhomogeneous ceramic samples requires matrix-defined scientific protocols to control matrix effects which reduce the sensitivity and precision of the instrumentation. Quantification of the measured fluorescence intensities into absolute concentration values and detection of light elements is encumbered by the lack of matrix matched calibration and proper vacuum facilities. Nevertheless, semi-quantitative values for a limited range of high Z elements can be generated. Unstandardized results are difficult to validate by others, and decreased analytical resolution of non-destructive surface analysis may disadvantage site-specific sourcing, jeopardize correct group assignments, and lead to under-interpretation of ceramic craft and production systems.