A set of about 70 fresco samples made with pigments and binders typical of the Renaissance period in Rome has been characterized by LIBS, LIF and colorimetric measurements in order to build an as much as possible complete database. Aiming at providing the restorers and art historians with a useful tool for the study of ancient frescoes, the samples have been prepared in agreement with the Cennino Cennini recipes for both materials and procedures. Afterward, the obtained spectral data have been processed by means of multivariate analysis methods in order to find the most significant features that can help in fast characterization and recognition of real unknown specimens.