Developing good performance and low-cost oxygen permeable membranes for CO2 capture based on the oxy-fuel concept is greatly desirable but challenging. Despite tremendous efforts in exploring new CO2-stable dual-phase membranes, its presence is however still far from meeting the industrial requirements. Here we report a series of new Ca-containing CO2-resistant oxygen transporting membranes with composition 60wt.%Ce0.9Ln0.1O2-40wt.%Ln0.6Ca0.4FeO3(CLnO-LnCFO; Ln = La, Pr, Nd, Sm) synthesized via a Pechini one-pot method. Our results indicate all investigated compounds are composed of perovskite and fluorite phases, while the perovskite phases in the CNO-NCFO and CSO-SCFO membranes after sintering generates Ca-rich and Ca-less two kinds of grains with different morphologies, where the Ca-less small perovskite grains block the transport of oxygen ions and eventually result in poor oxygen permeability. Among our investigated CLnO-LnCFO membranes, CPO-PCFO exhibits the highest oxygen permeability and excellent CO2 stability, which were mainly associated with the improvement in crystal symmetry, non-negligible electronic conductivity of fluorite phase and the enhancement in electronic conductivity of perovskite. Our results establish Ca-containing oxides as candidate material platforms for membrane engineering devices that combine CO2 capture and oxygen separation.