The various application possibilities of microscopic x‐ray fluorescence and associated methods for the characterization and provenance analysis of objects and materials of cultural heritage value are discussed by means of a number of case studies. They include the trace analysis of historic glass, the analysis of corroded coins and statues in bronze and silver and the study of inks on historical documents. These studies are conducted by means of micro‐XRF instruments installed at synchrotron beamlines and by means of laboratory equipment, some of which is easily transportable to the museum or archaeological site where the objects of interest are located. Copyright © 2000 John Wiley & Sons, Ltd.