A novel porous N-doped carbon microsphere (polymer-dopamine derived carbon, PDA-C) with high specific surface area was synthesized as sulfur host for high performance of lithium-sulfur batteries. We used KOH to adjust the pore size and surface area of the PDA-C materials, and then impregnated sulfur into the PDA-C samples by vapor-melting diffusion method. Effects of pore size of the PDA-C samples on the electrochemical performance of the PDA-C@sulfur cathodes were systematically investigated. Raman spectra indicated an enhanced trend of the degree of graphitization of the PDA-C samples with increasing calcination temperature. The surface area of the PDA-C samples increases with amount of the KOH in the pore-creating process. The graphitized porous N-doped carbon provides the high electronic conductive network. Meanwhile, the PDA-C with high surface area and uniform micropores ensures a high interaction toward sulfur as well as the high dispersion of nanoscale sulfur layer on it. The microporous PDA-C@S cathode material exhibits the excellent high rate discharge capability (636mAhg−1 at 2.0C) and good low/high-rate cycling stability (893mAhg−1 (0.5C) and 608mAhg−1 (2.0C) over 100 and 300 cycles). Cyclic voltammogram curves and electrochemical impedance plots show that both the impedance and polarization of the cells increase with decreasing pore size.