The shuttle effect hinders the practical application of lithium-sulfur (Li-S) batteries due to the poor affinity between a substrate and Li polysulfides (LiPSs) and the sluggish transition of soluble LiPSs to insoluble LiS or elemental S. Here, we report that Ni hexatomic clusters embedded in a nitrogen-doped three-dimensional (3D) graphene framework (Ni-N/G) possess stronger interaction with soluble polysulfides than that with insoluble polysulfides. The synthetic electrocatalyst deployed in the sulfur cathode plays a multifunctional role: (i) selectively adsorbing the polysulfides dissolved in the electrolyte, (ii) expediting the sluggish liquid-solid phase transformations at the active sites as electrocatalysts, and (iii) accelerating the kinetics of the electrochemical reaction of multielectron sulfur, thereby inhibiting the dissolution of LiPSs. The constructed S@Ni-N/G cathode delivers an areal capacity of 9.43 mAh cm at 0.1 C at S loading of 6.8 mg cm, and it exhibits a gravimetric capacity of 1104 mAh g with a capacity fading rate of 0.045% per cycle over 50 cycles at 0.2 C at S loading of 2.0 mg cm. This work opens a rational approach to achieve the selective adsorption and expediting of polysulfide transition for the performance enhancement of Li-S batteries.