To exploit the high energy density of lithium-sulfur batteries, porous carbon materials have been widely used as the host materials of the S cathode. Current studies about carbon hosts are more frequently focused on the design of carbon structures rather than modification of its properties. In this study, we use boron-doped porous carbon materials as the host material of the S cathode to get an insightful investigation of the effect of B dopant on the S/C cathode. Powder electronic conductivity shows that the B-doped carbon materials exhibit higher conductivity than the pure analogous porous carbon. Moreover, by X-ray photoelectron spectroscopy, we prove that doping with B leads to a positively polarized surface of carbon substrates and allows chemisorption of S and its polysulfides. Thus, the B-doped carbons can ensure a more stable S/C cathode with satisfactory conductivity, which is demonstrated by the electrochemical performance evaluation. The S/B-doped carbon cathode was found to deliver much higher initial capacity (1300 mA h g(-1) at 0.25 C), improved cyclic stability, and rate capability when compared with the cathode based on pure porous carbon. Electrochemical impedance spectra also indicate the low resistance of the S/B-doped C cathode and the chemisorption of polysulfide anions because of the presence of B. These features of B doping can play the positive role in the electrochemical performance of S cathodes and help to build better Li-S batteries.