(Ca2+, V5+) co-doped Y2Ti2O7 yellow pigments were prepared by solid route. The influence of the annealing temperature, the vanadium rate (0.02 <= x <= 0.3) and a post-mechanical grinding on the phase purity and the colour were studied using X-ray diffraction and UV-vis spectroscopy. The correlation between pigment colouration, synthesis parameters and structural feature is then discussed. Pigments with various colourations from yellow to deep orange can be obtained depending on the synthesis parameters linked to a slight modification of the vanadium coordination environment. For a same composition, the pigment colouration depends on the creation of Frenkel pairs inside the structure corresponding to a displacement of an oxygen atom toward one interstitial empty site. (C) 2009 Elsevier Ltd. All rights reserved.