The heterogeneous oxidation of azo dye Reactive Black B (RBB) by the photo-Fenton system catalyzed with an immobilized iron oxide, B1 (supported with SiO2 grain), was investigated. Reactive Black B oxidation was carried out in an expended-bed reactor in which the effect of B1 dosage on the decolorization and degradation of RBB was examined. Through pseudo-first-order kinetic studies, decolorization was found to be faster than degradation with a fixed rate constant ratio. By determining the iron dissolution from B1, RBB oxidation was supposed to mainly occur on the B1 surface, which catalyzed the generation of hydroxyl radicals in the photo-Fenton reaction. Accordingly, the efficiency of photo-Fenton could reach 100% and 91.2% of decolorization and degradation, respectively, in 300 minutes.