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Detailed structural characterization and identification of key chemical constituents can uncover important information on historical and artistic significance of artworks and archaeological findings. The most difficult task during the process of painting investigation is the identification of pigments and bindings included in structure of the ground and paint layers. In the last decades, significant achievements in analytical science and instrumentation have led to a steadily increasing use of state-of-the-art analytical techniques in this field. Such powerful technique as X-ray material and structure analysis has some restrictions. In this context, laser-induced breakdown spectroscopy (LIBS), a rapid elemental analysis technique, which is applicable in situ and is nearly nondestructive, offers a potential alternative to X-ray fluorescence, which sometimes is not really non-destructive. The LIBS instrumentation used in our work is quite standard and relies on the use of multichannel detection for recording the time-, spatially, and spectrally resolved emission, produced by focusing a single laser pulse on a surface of the sample under study. Material consumption in our LIBS experiment is minimal (estimated volume is around 10-8 cm3 for a typical crater 5-10 micron deep and 50-100 micron wide), and any damage to the sample's surface is practically invisible to the naked eye. The funds of the main Belarussian museums contain a large number of non-identified and non-attributed archaeological and art objects of European value including items found in the territory of Belarus or imported into it. As typical archaeological objects with composite matrix, fragments of bracelets (presumably with a glass basis) have been chosen. The LIBS technique has been also applied for the layer-by-layer pigment material microanalysis of non-attributed paintings as well as of problematic sections of well known paintings of famous artists.