In this paper, we propose a new strategy to develop high performance sulfur electrode by impregnating sulfur into the micropores of a Li+-insertable carbon matrix with the simultaneous use of a carbonate electrolyte, which does not dissolve polysulfides, to restrain the solution of the reaction intermediates of sulfur. To proof this concept, we prepared a Li+-insertable microporous carbon–sulfur composite by vaporizing sulfur into the micropores of the nanofiber-wired carbon microspheres. The experimental results demonstrate that, in the carbonate electrolyte of 1M LiPF6/PC-EC-DEC, such S/C composite electrode exhibits not only stable cycling performance with a reversible capacity of 720mAhg−1 after 100 cycles, but also superior high coulombic efficiency of ∼100% upon extended cycling (except the first three cycles). The structural and electrochemical analysis indicates that the improved electrochemical behaviors of the S/C composite arise from a new reaction mechanism, in which Li+ ions and electrons transport through the carbon matrix into the interior of the cathode and then react with the embedded sulfur in the S/C solid–solid interfaces, avoiding the solution of the intermediates into the bulk electrolyte. More significantly, the structural design and working mechanism of such a sulfur cathode could be extended to a variety of poorly conductive and easily soluble redox-active materials for battery applications.