A concise insight into the outputs provided by the latest prototype of visible‐near infrared (Vis‐NIR) multispectral scanner (National Research Council‐National Institute of Optics, CNR‐INO, Italy) is presented. The analytical data acquired on an oil paintingMadonna of the Rabbitby É. Manet are described. In this work, the Vis‐NIR was complemented with X‐ray fluorescence (XRF) mapping for the chemical and spatial characterization of several pigments. The spatially registered Vis‐NIR data facilitated their processing by spectral correlation mapping (SCM) and artificial neural network (ANN) algorithm, respectively, for pigment mapping and improved visibility ofpentimentiand of underdrawing style. The data provided several key elements for the comparison with a homonymous original work by Titian studied within the ARCHive LABoratory (ARCHLAB) transnational access project.