This study was conducted to research the formation and the color development of NiO-ZnO-Fe2O3-TiO2-SnO2 system for the purpose of synthesizing the spinel pigments which are stable at high temperature. After preparing ZnO-Fe2O3 as a basic composition, {{{{ chi }}NiO.(l-{{{{ chi }})ZnO.Fe2O3 system, {{{{ chi }}NiO.(l-{{{{ chi }})ZnO.TiO2 system, and {{{{ chi }}NiO.(l-{{{{ chi }})ZnO.SnO2 system were prepared with {{{{ chi }}=0, 0.2, 0.5, 0.7, 1 mole ratio respectively. The manufacturing was carried out at 128$0^{circ}C$ for 30 minutes. The reflectance measurement and the X-ray analysis of these specimens were carried out and the results were summarized as follows. 1. In the specimens which included NiO, it was difficult for the spinel structure to be formed. 2. As increasing the contents of NiO and Fe2O3, all the groups which were yellow or green colored changed to brown. 3. NiO-ZnO-Fe2O3 system and NiO-ZnO-TiO2 system formed the spinel structure and the illmenite structure appeared in NiO-TiO2 system.