Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries (LSBs). Here, we present a solution through far-reaching long-range electronic regulation (LRER) on single-atom active sites. N-doped carbons (Co-NC) are implanted with densely-distributed Co single atoms, and supported on Ti3C2Tx MXene substrates to assemble 3D Co-NC/MXene catalyst. MXene effectively mediates interlayer charge transfer (∼0.70 |e|) contrasted with popular carbon materials (∼0.06 |e|) to produce LRER through surrounding carbon atoms. The synergy of LRER with near-range electronic regulation (NRER) tunes electronic structures, and enhances heterostructural stability, thus provoking desirous catalytic kinetics of Co single atoms in sulfur reduction. Thereby, the Co-NC/MXene/S cathodes exhibit impressive rate performance and excellent cycling stability (only 0.015% capacity decay per cycle over 600 cycles at 4 C) in LSBs, surpassing state-of-the-art sulfur cathodes. This work reveals the importance of LRER for improved catalysis, and provides new guidance to tailor heterostructures to achieve high-efficient catalysts in various process.