The structure and the room temperature performances of sulfur cathodes composed of sulfur, carbon, and poly(ethylene oxide) (PEO) binder were studied with varying preparation method and binder content. Two different methods, ball mixing and mechanical stirring, were employed for preparation of slurry to obtain morphologically different cathodes. The cathodes prepared with mechanical stirring (SC cathodes) revealed more porous structure than those with ball mixing (BC cathodes). Scanning electron microscopy observations showed that sulfur particles were covered with dense and thick PEO film in the BC cathodes, whereas sulfur particles were bonded with porous PEO film in the SC cathodes. The SC-based cells exhibited much higher discharge capacity yielding 75% of sulfur utilization than the BC-based cells. The difference of discharge behaviors with different mixing methods indicates that the porosity of the cathode and the morphology of PEO binder are highly important factors for favorable electrochemical performance of lithium sulfur batteries. The cycle life of the SC-based cell was improved with the increase of binder content and with the roll pressing due to the increase of adhesiveness and cohesiveness of the sulfur cathode.