The potential of fibre optic reflection infrared spectroscopy for the non-invasive identification of artists’ pigments is presented. Sixteen different carbonate, sulphate and silicate-based pigments are taken into account considering their wide use during the history of art and their infrared optical properties. The infrared distortions mainly generated by the specular reflection are discussed on the basis of experimentalmeasurements carried out on reference samples. The study on pure materials permitted the definition of marker bands, mainly combination and overtone modes, enhanced by the diffuse reflection component of the light, functional for the non-invasive pigment identification in real artworks. Several case studies are reported, including wall, easel, canvas paintings and manuscripts from ancient to modern art demonstrating the strengths of the technique on the identification of pigments even in the presence of complex mixtures of both organic (binders, varnishes) and inorganic (supports, fillers and other pigments) compounds.