Applications of advanced cathode materials with well-designed chemical components and/or optimized nanostructures promoting the sulfur redox kinetics and suppressing the shuttle effect of polysulfides are highly valued. However, in the case of actual lithium-sulfur (Li−S) batteries under practical working conditions, one long-term obstacle still exists, which is mainly due to the difficulties in massive synthesis of such nanomaterials with low cost and ease of control on the nanostructure. Herein, we develop a facile synthesis of carbon coated Ti₄O₇ hollow nanoparticles (C−Ti₄O₇) using spherical polymer electrolyte brush as soft template, which is scalable via utilizing a minipilot reactor. The C−Ti₄O₇ hollow nanoparticles provide strong chemical adsorption to polysulfides through the large polar surface and additional physical confinement by rich micro- & mesopores and have successfully been employed as an efficient sulfur host for multilayer pouch cells. Besides, the sluggish kinetics of the sulfur and lithium sulfide redox mechanism can be improved by the highly conductive Ti₄O₇ via catalyzation of the conversion of polysulfides. Consequently, the C−Ti₄O₇ based pouch cell endows a high discharge capacity of 1003 mAh g⁻¹ at 0.05 C, a high-capacity retention of 83.7 % after 100 cycles at 0.1 C, and a high Coulombic efficiency of 97.5 % at the 100th cycle. This work proposes an effective approach to transfer the synthesis of hollow Ti₄O₇ nanoparticles from lab- to large-scale production, paving the way to explore a wide range of advanced nanomaterials for multilayer Li−S pouch cells.