Abstract: In the processing of high ash content sludge using chemical looping technology, the interaction and flow dynamics between sludge ash and oxygen carriers are unavoidable. This raises important questions regarding whether the iron-rich sludge ash, which contains active components such as Fe2O3, exhibits synergistic oxygen-carrying properties and contributes to the stability of iron-based oxygen carriers. This study investigates the thermal behavior of industrial-scale prepared CaMn0.5Fe0.5O3-δ perovskite oxygen carriers (POC), iron-rich sludge ash (SA), and a 50POC/50SA mixture through thermogravimetric analysis (TGA) under a 5% H2 atmosphere. We examined the isothermal reaction kinetics of the oxygen release process for these three materials. The results indicate that the presence of SA somewhat delays the oxygen decoupling process of POC, with the weight loss during oxygen release slightly exceeding the theoretical weighted value, which diminishes with increasing temperature. The activation energy (Ea) for the oxygen release reaction of the mixed sample is calculated to be 46.135 kJ/mol, which is 1.973 kJ/mol lower than the theoretical weighted value. It suggests a positive synergistic effect between SA and POC upon mixing, enhancing the oxygen-carrying capacity and reactivity of the perovskite oxygen carrier. Therefore, the iron-rich SA plays a significant role in the oxygen-carrying performance during the chemical looping conversion of sludge.