Abstract The method of the laser ablation-inductively coupled plasma-mass spectrometry has become an effective tool in the analysis of the art and archaeological objects. With a few exceptions, however, it has not been fully established in the provenance analysis of historical paintings yet. Although the method is micro-destructive for the paint samples, the direct solid sample analysis with just a minor material removal enables obtaining valuable information on the trace element composition, which is useful for the track the origin of mineral pigments, as, e.g. the clay-based pigments. This work aimed for the optimization of the measurement parameters and a subsequent differentiation of red clays from three reference localities in Europe that were pre-selected based on their relevance for the 18th century painting. Finally, the ground preparatory layer from a painting by an 18th century painter, J. G. de Hamilton, has been analysed. It was satisfactorily proved that the red clay used in the ground was mined out in Troschenreuth, Bavaria, Germany. This is in line with the historical documents recording that Hamilton, when he was acting in Bohemia, bought already primed (ready-to-use) canvases in Bavaria. Despite the heterogeneity and small sizes of paint samples the obtained results show the way in which the provenance analysis of clays in paint samples can be performed. This opens up an entirely new possibility of assessing the regional provenance of historical paintings.