This paper presents the novel application of recently developed analytical techniques to the study of paint layers on sculptures that have been restored/repainted several times across centuries. Analyses were performed using portable XRF, mu-XRD and mu-Raman instruments. Other techniques, such as optical microscopy, SEM-EDX and mu-FTIR, were also used. Pigments and other materials including vermilion, minium, red lac, ivory black, lead white, barium white, zinc white (zincite). titanium white (rutile and anatase), lithopone, gold and brass were detected. Pigments from both ancient and modern times were found due to the different restorations/repaintings carried out. mu-Raman was very useful to characterise some pigments that were difficult to determine by mu-XRD. In some cases, pigments identification was only possible by combining results from the different analytical techniques used in this work. This work is the first article devoted to the study of sculpture cross-section samples using laboratory-made mu-XRD systems.