Porous spherical carbons (PSCs) with tunable pore structure (pore volume, pore size, and surface area) were prepared by an aerosol-assisted process. PSC/sulfur composites (PSC/S, S: ca.59 wt %) were then made and characterized as cathodes in lithium/sulfur batteries. The relationships between the electrochemical performance of PSC/S composites and their pore structure and particle morphology were systematically investigated. PSC/S composite cathodes with large pore volume (>2.81 cm(3)/g) and pore size (>5.10 nm) were found to exhibit superior electrochemical performance, likely due to better mass transport in the cathode. In addition, compared with irregularly shaped carbon/sulfur composite, the spherical shaped PSC/S composite showed better performance due to better electrical contact among the particles.