A detailed characterization of painting materials by Raman and time-gated laser-induced fluorescence (TG-LIF) spectroscopy is proposed. The complementary capabilities of the considered techniques are investigated on a set of laboratory samples realized simulating real artworks. The achieved results confirmed the capability of Raman spectroscopy to characterize pigments and dyes, while the identification of binders and protective materials proved to be difficult because of their intense fluorescence. For this reason, the analyzed samples were also classified by TG-LIF spectroscopy in terms of their characteristic emission wavelengths and decay times. The complementary capabilities of Raman and TG-LIF techniques are confirmed, and a correlati...