A ceramic pigment with nominal composition Ti0.97Cr0.015Sb0.015O2 was prepared by microemulsion-mediated solvothermal method at 180 °C. Anatase or rutile single phase was obtained depending on the synthesis conditions. Scanning electron microscope analysis showed the formation of spheres with particle size around 600 nm. The anatase to rutile transformation temperature was determined by XRD and Raman spectroscopy. The evolution of the colour was studied, and it was related with the polymorphic transition. Yellow pigments were obtained at low temperature and huge orange colour was observed at high temperature. Powders prepared at 180 °C were tested with an industrial frit. Similar chromatic coordinates of an industrial orange ceramic pigment obtained at high temperatures were observed. ζ-potential values of the particles were ∼−57 mV. The size, shape, colour and electrostatic stability of these particles make them potential candidates to be applied in glazes or inkjet printers as orange ceramic pigments.