AbstractLithium‐sulfur (Li–S) batteries are facing a multitude of challenges, mainly pertaining to the sluggish sulfur redox kinetics and rampant lithium dendrite growth on the cathode and anode side, respectively. In this sense, MXene has shown conspicuous advantages in serving as a dual‐functional promotor for Li–S batteries throughout the morphologic engineering, but still suffers from poor electrocatalytic activity and insufficient lithophilic sites. Herein, atomically dispersed Co sites are seeded onto the size effect‐enabled V2C MXene spheres (Co‐VC), leading to the generation of unique coordination configurations and rich active sites. Electrochemical tests combined with synchrotron radiation X‐ray 3D nano‐computed tomography and theoretical calculations unravel that Co‐VC with optimal coordination environments simultaneously boost sulfur reaction kinetics and lithium nucleation. As a consequence, Li–S batteries with Co‐VC modified separator can sustain a stable operation over 700 cycles with negligible capacity decay at 1.0 C, and delivers an areal capacity of 9.0 mAh cm−2 and desired cyclic performance at a high sulfur loading of 7.6 mg cm−2 with a lean electrolyte dosage of 4.0 µL mgS−1 at 0.1 C. The work opens a new avenue for boosting atomic‐scale site design with the aid of 2D substrates toward pragmatic Li–S batteries.