In the pursuit of decarbonizing transportation sectors, there has been considerable enthusiasm from both industries and academia regarding the utilization of atmospheric CO2 as a chemical feedstock. To mitigate the energy requirements associated with carbon capture, utilization, and sequestration, research efforts are focused on developing and exploring electrochemical cell technologies. Here, we present an innovative solid oxide electrochemical cell configuration featuring a hybrid electrolyte membrane electrode assembly (HE-MEA) designed for efficient CO2 capture and separation. Our approach involves optimizing the process through the tuning of electrolyte and electrode compositions and operation conditions, aiming to capture CO2 effectively under various conditions. The investigation of the cathode's working mechanism, employing advanced characterization techniques, will be presented. This study marks a significant step forward in CO2 capture, particularly at elevated temperatures, and contributes to the broader effort of advancing sustainable practices in transportation and combating climate change.