The formations of spinel and colors of ZnO-Fe2O3-TiO2-SnO2 system have been researched on the basis of ZnO-Fe2O3 system. Specimens were prepared by substituting Fe3+, with Ti4+ or Sn4+ when mole ratios between Fe3+ and Ti4+ or between Fe3+ and Sn4+ were 0.2 mole. The reflectance measurement and X-ray diffraction analysis of the formation of spinel and the colors of there specimens were carried out. ZnO-Fe2O3 system in which Fe2O3 was substituted with SnO2 and TiO2 was formed the spinel structure of 2ZnO.TiO2, 2ZnO.SnO2, ZnO.Fe2O3. The stable stains which were colored with yellow and brown could be manufactured.