The rarity and limited size of fragments from ancient and artistic objects (when available) make the use of non-invasive methods preferable, hence the success of methods based on light-matter interactions. The heterogeneity of  these materials requires the application nano-probes. The complexity of the materials (inorganic + organic, crystallized + amorphous, major to trace) requires the combination of several complementary analytical techniques (to probe elements, metallic species, organic molecular groups and crystalline structures) performed in imaging mode with sub-micrometric resolution, to reveal the relative localisation and interdependence of the different compounds. All these reasons explain the success of the ID21 instruments in the field of Cultural Heritage. Besides, challenges associated with these materials encourage us to further develop our instruments and some of the hardware and software developments presented here have been implemented with targeted applications to cultural heritage. Here are also presented review publications related to applications of synchrotron techniques for the analyses of artworks.