In the present study we carried out an extensive non-destructive and micro-destructive surface investigation on ancient decorated Sicilian samples of cultural interest, using a combination of different spectroscopic methods. In particular, the elemental composition, obtained by a handheld XRF analyser, acted as a valuable guideline for subsequent targeted sampling actions, thus minimizing the sampling damage. Hence, some questions not answered by XRF measurements (identification of some pigments, preparation layers, etc.) were subsequently resolved using Scanning Electron Microscopy coupled with Energy-Dispersive Spectrometry (SEM-EDS) and Fourier Transform Infrared absorbance spectroscopy (FT-IR). This multi-technique approach allowed us to provide useful information to establish the pigments and the production technique used by the craftsmen. [ABSTRACT FROM AUTHOR]