The porous cathode is a crucial component of LiO2 batteries, and its porous structure significantly impacts the battery's performance. In this study, a stacked porous cathode was fabricated via roller pressing. The influence of the cathode structure on the battery performance and mass transfer characteristics were examined using experimental and simulation methods. The structural characteristics, electrochemical properties, and overall battery performance of the stacked porous cathode were analyzed. Furthermore, the effects of the cathode structure on mass transfer within the cathode and battery performance were explored through numerical simulation. The results indicate that when the mass ratio of CNTs to ACET on the diaphragm side is 5:1, the cathode exhibits optimal structural parameters, with an average pore size of 24 nm and a maximum pore volume of 0.85564 cm3/g. Concurrently, the battery demonstrates an exceptionally high area specific capacity of 30.35 mAh/cm2. Integrating the simulation findings, it was observed that adjusting the structural parameters of the cathode enhances material transfer efficiency, thereby improving battery performance.