Image spectroscopy (IS) is an important tool for the noninvasive analysis of works of art. It generates a wide sequence of multispectral images from which a reflectance spectrum for each imaged point can be recovered. In addition, digital processing techniques can be employed to divide the images into areas of similar spectral behavior. An IS system designed and developed in our laboratory is described. The methodology used to process the acquired data integrates spectral analysis with statistical image processing: in particular, the potential of principal-component analysis applied in this area is investigated. A selection of the results obtained from a sixteenth-century oil-painted panel by Luca Signorelli is also reported.