The starting point of this project was to bridge the gap between the Departments of Analytical Chemistry and Archaeology. Archaeology has evolved from a more historically and art-historically orientated field of research to a fully emancipated science, comfortably adopting GIS, 3D modelling and chemical analysis to serve its own needs. The rapidly evolving field of XRF (X-ray fluorescence) analysis and the development of a new generation of lightweight, high-performance handheld XRF analysers promised new possibilities for in situ elemental determination. The primary aim of this research project was to evaluate the applicability of such a handheld XRF analyser when used in archaeological contexts and to develop a comprehensible protocol for data-processing. To fulfil these objectives, the Olympus Innov-X handheld XRF analyser was obtained and characterised and a work methodology was developed applying established lab protocols used in analytical chemistry. This instrument was then employed in three archaeological case studies where it investigated respectively the provenance of post-medieval Flemish stove-tiles, the origin and distribution of Iron Age red-painted pottery from Mount Kemmel and related sites, and the geochemical composition of archaeological soil features in the Yustyd valley (Russia) during excavations in 2011. The research combined different XRF techniques, with a central role for handheld XRF spectrometry in all selected archaeological applications. In addition, the measurements of both µ-XRF (micro-XRF) and TXRF (Total Reflection XRF) were used to act as a point of reference for the handheld measurements, since reference materials for the archaeological materials under focus are not available, and Raman spectroscopy was used to characterize the pigment in the red-painted pottery. Methodology and characterization of handheld XRF analysers The first part of this thesis consists of three chapters which deal with X-ray fluorescence in general and the instrumentation and methodology that were used ...