The accurate identification of pigments is of principal relevance in the field of cultural heritage conservation and restoration practices. In this preliminary study, a first attempt to set up a procedure for accurate red pigment identification, based on the assessment of the correlations existing between visible reflectance spectrometry (vis-RS) and Raman data, is presented. The proposed approach involved the realization of a library consisting of data acquired on a set of 35 pure red historical pigments supplied by ©Kremer Pigmente. In particular, vis-RS data, collected through a Konica Minolta CM-2600d spectrophotometer, were registered, together with the position of the Extrema Points (E.P.s) encompassing both the maximum and minimum points of the first derivative of the % spectral reflectance factor (SRF%) curves. Portable Raman spectroscopy measurements were collected by a B&W Tek Inc. portable Raman spectrometer equipped with a 785 nm laser. For each tested pigment, the positions and relative intensities of the characteristic Raman peaks were considered. The library was then tested for the characterization of the red/reddish painted areas of the medieval wall painting located within The Norman Castle of Aci Castello (Catania, Italy), and was shown to be essential for the unambiguous identification of the pigment used. It is worth noting that this study represents the first novel attempt to establish a reliable and efficient methodology for pigment identification, offering promising prospects in reducing uncertainties and ambiguities arising from the application of a single stand-alone approach.