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Nuclear techniques and other techniques using ionising radiation represent a valuable tool in non-destructive diagnostics applied to archaeological finds and objects of arts, namely for determining the composition of materials used in the production of artefacts. X-ray fluorescence analysis, both in its energy form and in its wave dispersive form, is one of the most widespread methods using ionising radiation to study the elemental composition of materials. It is frequently used for studies of various cultural and historic relicts and objects of art. This work summarizes the authors’ experience with X-ray fluorescence analysis in investigating historical frescos namely by means of portable provide spectroscopic devices. The results of these measurements information on the composition of the pigments, enable the comparison of processes used in the fabrication of pigments by individual artists, and in many cases offer information on how to repair the damaged parts.