This study was conducted to research the formation and the color development of CoO-ZnO-Fe2O3-TiO2-SnO2 system for the purpose of synthesizing the spinel pigments which are stable at high temperature. After preparing CoO-ZnO-Fe2O3, in which CoO causes the color, as a basic composition, $chi$CoO.(1-$chi$)ZnO.Fe2O3 system, $chi$CoO.(1-$chi$)ZnO.TiO2 system and $chi$CoO.(1-$chi$)ZnO.SnO2 system were prepared with $chi$=0, 0.2, 0.5, 0.7, 1.0 mole ratio respectively. The manufacturing was carried out at 128$0^{circ}C$ for 90 minutes. These specimens were analyzed by the reflectance measurement and the X-ray diffraction analysis and the results were summarized as follows: 1. All of the specimens formed the spinel structure and were colored with stable yellow or blue. 2. As the content of CoO and Fe2O3 in the specimens being increased, the reflectance of each specimen was measured becoming lower and the colors were changed from yellow to greyish blue and from blue to dark blue. 3. As the substituting amount of Co2+ ion for Zn2+ ion in $chi$CoO-ZnO-TiO2-SnO2 system being increased, the colors were changed from blue to greyish blue. The colors were changed from yellow to grayish green owing to the tetrahedral Co2+ ions being increased, the octahedral Co2+ ions being decreased with increasing the amount of Sn4+ ions. 4. CoO-ZnO-Fe2O3-TiO2-SnO2 system, in which Zn2+ was substituted with Co2+ and Fe3+ was substituted with Ti4+ and Sn4+, easily formed the spinel structure without regard to the amount of substitution or the ion owing to the selectivity of the coordination number: 4 of Zn2+, 4 of Co2+, 6 of Fe3+ or 6 of Ti4+ and Sn4+.