The commercialization of ultrahigh capacity lithium−oxygen (Li−O 2 ) batteries is highly dependent on the cathode architecture, and a better understanding of its role in species transport and solid discharge product (i.e., Li 2 O 2 ) formation is critical to improving the discharge capacity. Tailoring the pore size distribution in the cathode structure can enhance the ion mobility and increase the number of reaction sites to improve the formation of solid Li 2 O 2 . In this work, the potential of hierarchical zeolitetemplated carbon (ZTC) structures as novel electrodes for Li−O 2 batteries was investigated by using reactive force field molecular dynamics simulation (reaxFF-MD). Initially, 47 microporous zeolite-templated carbon morphologies were screened based on microporosity and specific area. Among them, four structures (i.e., RHO-, BEA-, MFI-, and FAU-ZTCs) were selected for further investigation including hierarchical features in their structures. Discharge product cluster analysis, self-diffusivities, and density number profiles of Li + , O 2 , and dimethyl sulfoxide (DMSO) electrolyte were obtained to find that the RHO-type ZTC exhibited enhanced mass transfer compared to conventional microporous ZTC (approximately 31% for O 2 , 44% for Li + , and 91% for DMSO) electrodes. This is due to the promoted formation of small-sized product clusters, creating more accessible sites for oxygen reduction reaction and mass transport. These findings indicate how hierarchical ZTC electrodes with micro-and mesopores can enhance the discharge performance of aprotic Li−O 2 batteries, providing molecular insights into the underlying phenomena.