A novel method for the preparation of Li₂S integrated into porous carbon black as host material by using a facile solution-based chemical process is described. Li₂S was synthesized by disproportionation of a Li₂S₆ polysulfide solution. The combination of a homogeneous Li₂S distribution with small Li₂S particle size and good contact with the carbon surface leads to ideal properties for the application in high-energy-density long-cycle-life lithium-sulfur batteries. An initial discharge capacity of 1259 mA h g⁻¹ _sulfur with good cycle stability as well as low polarization are achieved, rendering the novel method particularly suitable for application in full cells with silicon- or carbon-based anodes, which are used to overcome the main limitations observed using metallic lithium as anode in lithium-sulfur batteries.