This paper studies the antimony spreading and segregation that occurred along with the oxidation and solid-state reactions in the Fe2O3-Sb2O3 system. XRD, SEM, TG-DSC and particularly XPS were employed for characterizations. Sb2O4 and FeSbO4 are the only new phases detected. The formation of FeSbO4 is a more exothermic but slower reaction than oxidation of Sb2O3. A mechanical grinding of Sb2O3 and Fe2O3 leads to a significant dispersion of Sb2O3 possibly because of its low hardness. Dispersion of reference Sb2O4 in this way is negligible. During the heating of a mixture of Sb2O3 and Fe2O3 with an atomic ratio of Sb/Fe = 0.5 at 200-1000 degrees C in ambient air, the thermal spreading of Sb1O3 onto Fe 03 increases with increasing temperature until Sb2O3 is oxidized into Sb2O4. The surface atomic ratio of Sb/Fe measured by XPS, R-Sb/Fe, reaches a maximum around 400 degrees C. The complete oxidation of Sb2O3 leads to a decrease in RSb/Fe because of poorer dispersibility of Sb2O4. The formation of FeSbO4 starting at ca. 800 degrees C causes a further decrease in R-sb/Fe, but the R-Sb/Fe is still 3.2 times the nominal bulk Sb/Fe ratio when the Sb2O4 is completely transformed into FeSbO4.