The advent of inkjet printing (IJP) as the main used decoration technique for ceramic products has changed the technological requirements for pigments and the way they are obtained. To meet IJP and durability requirements, it is necessary to micronise the colourants to achieve particles smaller than 1 μm (median particle diameter d50 ∼300 nm). The high-energy milling process induces microstructural changes that affect the colour properties. In order to understand the effect of particle size reduction on chromatic properties, an in-depth study was carried out by simulating the industrial milling process on a pilot scale. The effect of micronisation was investigated for four ceramic pigments (yellow zircon, brown spinel, pink malayaite, and green eskolaite) and one dye (blue olivine) by UV–vis–NIR optical spectroscopy (DRS), chromatic coordinates and XRPD analyses (Rietveld method). This study was carried out on the colourants both as they were and mixed with glass, reproducing the industrial firing process. The results obtained led to the definition of the main aspects responsible for the colour evolution derived from the milling process.