Since the end of the 20th century, the α-, β- and ε-copper phthalocyanine (CuPc) blue pigments are widely used in modern artists' paints. The identification of the CuPc crystalline structure can provide useful technical and chronological information for the study of works of art. Although when a CuPc blue pigment is identified, its crystalline structure often remains unspecified despite the interest for conservation science. In this study, X-ray powder diffraction, attenuated total reflectance micro-Fourier transform infrared spectroscopy and micro-Raman spectroscopy analyses have been carried out on 15 dry pigment samples of CuPc and acrylic, vinylic, alkyd, arabic gum and oil-based artists' paints. By using the polymorphic markers underlined for dry pigments, the CuPc crystalline structure has been successfully identified for most of the analysed artists' paints. However, according to the analytical technique used and the investigated paint sample, the obtained results largely differ. Copyright © 2012 John Wiley & Sons, Ltd.