Lithium−sulfur (Li−S) battery is promising next generation rechargeable battery due to its potential high energy density. However, it suffers from major problems including poor cycle performance and low efficiency, mainly due to the high solubility of intermediate poly-sulfides and their side-reactions with the Li-anode.  Recently, we have developed various open-structure functional gradient C-S composite cathodes with very high S-loadings that can utilize the high energy density of S-cathode while minimize the migration of poly-sulfide to anode side. We employed scalable and industrial viable method such as layer-by-layer nano-assembly technique that leads to a binder-free, three-dimensional porous cathode via electrostatic attraction and enables the fabrication of Li−S cells with remarkably improved performance including a long cycle life exceeding 600 cycles and a high Coulombic efficiency of 97.5% at the 1 C rate. Moreover, our Li−S cells have presented a high rate response up to 2.5 C with high sulfur utilization (a reversible capacity of 1100 mAhg−1, 900 mAhg−1, 700 mAhg−1, and 450 mAhg−1 of sulfur at 0.3, 0.6, 1, and 2.5 C rates, respectively). The results provide important progress toward the understanding of the role of multilayered cathodes and the realization of high-efficiency and long-term service life for Li−S batteries.