Hierarchical TiO₂ micron spheres assembled by nano-plates were prepared through a facile hydrothermal route. Chemical tuning of the TiO₂ through hydrogen reduction (H-TiO₂) is shown to increase oxygen-vacancy density and thereby modifies the electronic properties. H-TiO₂ spheres with a polar surface serve as the surface-bound intermediates for strong polysulfides binding. Under the restricting and recapturing effect, the sulfur cathode could deliver a high reversible capacity of 928.1 mA h g⁻¹ after 50 charge-discharge cycles at a current density of 200 mA g⁻¹. The H-TiO₂ additive developed here is practical for restricting and recapturing the polysulfide from the electrolyte.