AbstractUncritical application of portable X‐ray fluorescence (PXRF) to non‐destructive analysis of archaeological ceramics has been received with scepticism. In this article, we present a methodological evaluation of the parameters and constraints for PXRF analysis of archaeological ceramics. We use experimental matrices that simulate characteristics of archaeological artefacts to demonstrate the impact of (1) surface morphology, (2) organic surface coatings and (3) grain size and mineralogy on non‐destructive PXRF analysis. We then apply these parameters to PXRF analysis of heterogeneous handmade ceramics from central Turkey. We conclude that with appropriate methodology, non‐destructive PXRF analysis can be demonstrated to provide a high level of accurate and precise geochemical discrimination for archaeological ceramics. Copyright © 2011 John Wiley & Sons, Ltd.