The main objective of this research is the development of totally nondestructive methodologies for the investigation of artworks. Proposes 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. Several representative inorganic artists' pigments (mainly until the Renaissance period) were considered; powder x-ray diffractograms and diffuse reflectance spectra in the visible, near-, middle-, and far-infrared range were recorded for pure pigments. Suitable samples were then prepared 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 results were used in the interpretation of the spectra obtained from some paintings collected in the Uffizi Gallery, Florence (Giotto and Luca Signorelli). The point-wise 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.