In the present work, a powerful tool for the investigation of paintings is presented. This permits the tuneable multispectral real time imaging between 200 and 5000 nm and the simultaneous multispectral acquisition of spectroscopic data from the same region. We propose the term infrared reflectoscopy for tuneable infrared imaging in paintings (Chryssonlakis and Chassery, The Application of Physicochemical Methods of Analysis and Image Processing Techniques to Painted Works of Art, Erasmus Project ICP-88-006-6, Athens, June, 1989) for a technique that is effective especially when the spectroscopic data acquisition is performed between 800 and 1900 nm. Elements such as underdrawings, old damage that is not visible to the naked eye, later interventions or overpaintings, hidden signatures, nonvisible inscriptions, and authenticity features can thus be detected with the overlying paint layers becoming successively “transparent” due to the deep infrared penetration. The spectroscopic data are collected from each point of the studied area with a 5 nm step through grey level measurement, after adequate infrared reflectance (%R) and curve calibration. The detection limits of the infrared detector as well as the power distribution of the radiation coming out through the micrometer slit assembly of the monochromator in use are also taken into account. Inorganic pigments can thus be identified and their physicochemical properties directly compared to the corresponding infrared images at each wavelength within the optimum region. In order to check its effectiveness, this method was applied on an experimental portable icon of a known stratigraphy.