Abstract Scanning x‐ray fluorescence (MA‐XRF), Reflectance Imaging Spectroscopy (RIS) and Luminescence Imaging Spectroscopy (LIS) are scientific methods extensively used in the investigation of artworks in Cultural Heritage Science. Nevertheless, these three highly complementary imaging methods have never been implemented in a single instrument. In this paper, we present a scanning system that is the first to simultaneously combine MA‐XRF, RIS, and LIS techniques, generating spatially aligned hyperspectral datasets. The specifications of the instrument and of the collected datacubes are described, together with the processing pipeline developed for the coupled exploitation and interpretation. The operation of this instrument, combining XRF with RIS and LIS mapping in an extended range (400–2500 nm and 200–1000 nm, respectively), is exemplified on an anonymous test painting, studied previously. A focus on a restored area of this painting allows to illustrates the complementarity of the three aforementioned methods, for the visualization and characterization of pigments, varnish, and binders.