ABSTRACTSX‐ray fluorescence analysis is a non‐destructive method, very useful for qualitative and quantitative determination of chemical elements in paintings, frescoes, enamels, etc.Measurements have been carried out on ancient Persian mural painting allowing the identification of about ten different pigments.Furthermore, many oil paintings have been examined. For example, about thirty regions of different colour tonalities concerning the ‘Deposizione’by Raffaello Sanzio have been analysed; in this way it has been possible to determine the composition of several pigments used by the author and to identify some restored regions.The enamels of a ligneous Egyptian panel have also been studied; the results are in good agreement with those obtained using conventional methods.