AbstractRemoving radioactive corrosion products from Cr-containing iron oxides require a multi-step and multi-cycle decontamination process. The present article brings out the effect of divalent metal ion substitution on the release rate of chromium in the oxidative pre-treatment step. The non-stoichiometric cobalt chromium ferrites were synthesized, characterized and effect of Zn2+/Ni2+ substitution on the dissolution behavior was probed. The dissolution rates decreased with increasing the degree of inclusion and showed minima at ~ 0.4–0.6 atom% which is explained on the basis of lattice structure. It is concluded that the dissolution kinetics of native nickel–chromium ferrites in reactors increases with metal ion inclusion.