A fluorine-free route has been developed to fabricate V/Pr co-doped zircon (ZrSiO4) ceramic pigments with Na3VO4 and Pr(NO3)3·6H2O as colourants. The as-prepared pigments were characterized by XRD, Raman, XPS, UV–vis, FE-SEM, TEM and automatic colourimeters. The results show that Na3VO4 can not only act as colourant to produce blue hue, but as mineralizer to accelerate the formation of V/Pr co-doped ZrSiO4 pigment. A colour tuning between blue, green and yellow can be achieved by increasing the mole ratio of Pr/V, and the most intense yellow hue (L* = 74.55, a* = −0.38, b* = 46.82) is obtained at a mole ratio of Pr/V = 0.5. Both Pr4+ and Pr3+ cations are co-existed in the pigments, where Pr4+ contributes to the generation of yellow hue while Pr3+ undermines the yellow hue. The good chromatic ability in glaze at high temperature suggest its potential application in ceramic decoration.