A willemite brown inorganic pigment was synthesized by subsyituting MnO for ZnO. The composition of MnxZn2-xSiO4 (X=0.1, 0.3, 0.5, 0.7 and 0.9mole) was synthesized at 1200~1300°C by solid state method. The characteristics of synthesized pigment were analyzed by X-ray diffraction, FT-IR spectroscopy, Raman spectroscopy and SEM. The UV- vis spectroscopy and CIE L*a*b* measurement were employed to analyzed color. Willemite single crystal phase was synthesized with compositions of Mn0.3Zn1.5SiO2 and Mn0.5Zn1.5 SiO2 from 1300°C/3h. The synthesized pigment of Mn0.5Zn1.5 SiO2 at 1300°C/3h was applicated to lime barium glaze and lime zinc glaze and the CIE L*a*b* values were 30.32, 7.17, 3.14 and 32.04, 8.18, 3.49, respectively.