This study aims to synthesize Cr doped Perovskite brown pigments. The pigment were synthesized by doping Cr2O3(0.01 ~ 0.05mole) for TiO2(0.993 ~ 0.963 mole) at 1150 ~ 1350°C. The samples were characterized by X-ray diffraction (XRD), Raman Spectrometer, Scanning Electron Microscope(SEM) and the UV/Vis spectroscopy. The optimum composition was CaCr0.03Ti0.978O3 and heating condition was 1300°C for 3h of soaking time. The doped Cr ion for Perovskite was observed to be Cr(Ⅲ) and Cr(Ⅳ). The brown color was mixed with violet doped by Cr4+(3A2 → 3T2) and Blueish-Green doped by Cr3+(4A2g → 4F1g). The results of SEM analysis showed the Perovskite structure and the particle size was approximately 2µm. The color in Frit 6060 glaze adding 10wt% pigment was Redish Brown, and CIE Lab parameters were L*= 41.53, a*=13.27 and b*=9.94 .