Oxyfuel process is a promising technique for carbon capture and storage, and a new application of perovskite-type oxide is as oxygen carrier for CO₂ capture in oxy-fuel combustion system. This study proposed a novelty process and an optimization study on the synthesis of the BaCoO_3−δ perovskite powders using microwave-assisted EDTA method. OA₁₆ (4⁵) orthogonal experiments were employed to optimize the process parameters such as precursor pH, microwave time, microwave power and calcination temperature. The oxygen production performance of synthesized powders were investigated in a fixed-bed reactor system. It was found that the order of significant factors for oxygen production performance of synthesized perovskite samples is microwave radiation time > pH value of precursor solution > calcination temperature > microwave power. Based on the results of the range analysis, the best oxygen production performance of BaCoO_3−δ was found at pH value of precursor solution was 8, microwave radiation time was 30 min, microwave power was 700 W and calcination temperature was 600 °C. Finally, the optimized sample was selected as candidate for multiple oxygen adsorption/desorption cycles tests. Results demonstrate that the prepared perovskites via optimized microwave-assisted EDTA process can be used as a potential oxygen carrier for oxyfuel combustion application.