Chemical Looping with Oxygen Uncoupling (CLOU) offers a potentially effective approach for converting solid carbonaceous fuels with inherent carbon dioxide capture. It utilizes oxygen carriers that allow facile and reversible exchange of their lattice oxygen with external environment under varying oxygen partial pressures. The varying and often tunable thermodynamic properties of mixed oxides of first row transition metals make them potentially viable for CLOU applications. In this study, mixed iron-cobalt and iron-manganese oxides are synthesized and evaluated in terms of their ability to uncouple oxygen. The effects of adding a secondary perovskite phase on the uncoupling properties of these primary transition metal oxides are also investigated. The experimental results indicate that different cation compositions exhibit different oxygen uncoupling properties. The initial decomposition temperature of the oxygen carrier sample is found to generally decrease with increasing amount of Co or Mn. Addition of a secondary perovskite phase is found to significantly affect oxygen donation properties of the primary mixed metal oxides. For instance, CLOU properties of mixed Fe-Co oxides are enhanced by perovskite addition. In contrast, oxygen carrying capacity of mixed Fe-Mn oxides under an isothermal condition is negatively affected by perovskite addition. Redistribution of the transition metal cations between the primary and secondary oxide phases is likely to be responsible for such changes in their redox properties. (C) 2014 Elsevier Ltd. All rights reserved.