Slow kinetics of polysulfide conversion reactions lead to severe issues for lithium–sulfur (Li–S) batteries, for example, low rate capability, polysulfide migration, and low Coulombic efficiencies. These challenges hinder the practical applications of Li–S batteries. In this study, we proposed a rational strategy of tuning the d-band of catalysts to accelerate the conversion of polysulfides. Nitrogen vacancies were engineered in hexagonal Ni₃N (space group P6₃22) to tune its d-band center, leading to the strong interaction between polysulfides and Ni₃N. Because of the greater electron population in the lowest occupied molecular orbital of Li₂S₄, the terminal S–S bonds were weakened for breaking. Temperature-dependent experiments confirm that Ni₃N_0.85 demonstrates a much low activation energy, thereby accelerating the conversion of polysulfides. A Li–S cell using Ni₃N_0.85 can deliver a high initial discharge capacity of 1445.9 mAh g^–1 (at 0.02 C) and low decay per cycle (0.039%). The Ni₃N_0.85 cell can also demonstrate an initial capacity of 1200.4 mAh g^–1 for up to 100 cycles at a high loading of 5.2 mg cm^–2. The high efficiency of rationally designed Ni₃N_0.85 demonstrates the effectiveness of the d-band tuning strategy to develop low-activation-energy catalysts and to promote the atomic understanding of polysulfide conversion in Li–S batteries.