Synthesis of gray ceramic pigment was carried out by doping cobalt on Tialite crystal structure. Tialite was synthesized by using Al2O3 and TiO2, and was doped with Co3O4 as a chromophore material. To prevent the thermal decomposition during cooling procedure Fe2O3 was added by 0.05mole as a stabilizer. Samples were fired at 1400~1500°C for 2hours and cooled naturally. Crystal structure, solubility limit and color of synthesized pigment were analyzed by XRD, Raman spectroscopy, UV and UV-vis. Yield percentage of Tialite was 96.15% with using Fe2O3 as a stabilizer. It was found that solubility limit of Co2+ in Tialite crystal was 0.03 mole% through analysis of XRD and Raman. By adding pigment with 0.03 mole% of Co2+ to lime-barium glaze, stabilized Dark Gray color glaze having 46.12, -1.26, 0.53 as CIE-L*a*b* was synthesized.