To correlate the carbon properties, e.g. surface area and porous structure, with the electrochemical behaviors of carbon/sulfur (C/S) composite cathodes for lithium-sulfur (Li-S) batteries, four different carbon frameworks including Ketjen Black (KB, high surface area and porous), Graphene (high surface area and nonporous), Acetylene Black (AB, low surface area and nonporous) and Hollow Carbon Nano Sphere (HCNS, low surface area and porous) are employed to immobilize sulfur (80 wt%). It has been revealed that high surface area of carbon improves the utilization rate of active sulfur and decreases the real current density during the electrochemical reactions. Accordingly, increased reversible capacities and reduced polarization are observed for high surface area carbon hosts such as KB/S and graphene/S composites. The porous structure of KB or HCNS matrix promotes the long-term cycling stability of C/S composites but only at relatively low rate (0.2 C). Once the current density increases, the pore effect completely disappears and all Li-S batteries show similar trend of capacity degradation regardless of the different carbon hosts used in the cathodes. The reason has been assigned to the formation of reduced amount of irreversible Li2S on the cathode as well as shortened time for polysulfides to transport toward lithium anode at elevated current densities. This work provides valuable information for predictive selection on carbon materials to construct C/S composite for practical applications from the electrochemical point of view. (C) 2013 The Electrochemical Society. All rights reserved.