A brief review of application of X-ray fluorescence analysis (XRFA) to fine and applied arts related to Czech cultural heritage is presented. The Department of Dosimetry and Application of Ionising Radiation of CTU-FNSPE has used XRFA in collaboration with various Czech institutions dealing with cultural history for many kinds of artefacts, (e.g., Roman and medieval brass, gemstones and noble metals from the sceptre of one of the faculties of the Charles University in Prague, millefiori beads, etc.). In some cases, a combination of various other techniques alongside XRFA was used for enhancing our knowledge of a measured object.