Using the Pechini method, pigments with spinel structure (Zn7Sb2O12)were synthesized by substitution of the cation Zn2+ by Co2+, in compounds with different concentrations of Sb2O3. The doping resulted in CoxZn(7–x)Sb2O12 phases(x=1–7) that were isomorphs to spinel, denominated as samples A and B. After thermal treatment at 400C for 1 h, the powders were characterized by thermogravimetry(TG) and differential thermal analysis (DTA). The results indicate a different behavior whena higher amount of Sb2O3 is used, due to the presence of a secondary phase (ilmenite).