The main objective of our research is the development of totally non-destructive methodologies for the investigation of art works. We propose the use of fiber optic reflectance spectroscopy (FORS) in the visible and near-infrared region as a tool for the identification of the pigments used in painting. We have considered several representative inorganic artists' pigments (mainly till the Renaissance period); powder X-ray diffractograms and diffuse reflectance spectra in the visible, near-, middle- and far-infrared range were recorded for pure pigments. Then we prepared suitable samples with the same pigments using fresco, tempera and oil techniques. The visible and near-infrared spectra of these samples were recorded using an optical fiber spectrum analyzer; color analysis (chromaticity, dominant wavelength and purity) was also performed. The obtained results were used in the interpretation of the spectra obtained from some paintings collected in the Uffizi Gallery, Florence (Giotto and Luca Signorelli). The pointwise information obtained by FORS analysis was also used to calibrate and tune an image spectroscopy system, based on sequences of band-pass filtered images in the near infrared range.