In article number 1902491, Yuwei Zhang, Li Niu, and co‐workers report a novel polysulfides immobilizer for Li–S batteries. 3D hierarchical nitrogen‐doped carbon nanosheets/molybdenum phosphide nanocrystal hollow nanospheres (MoP@C/N HCSs) not only provide strong physical trapping and chemical anchoring toward polysulfides, but also accelerate the kinetics of the polysulfides redox reaction and lower the Li2S nucleation/dissolution interfacial energy barrier and self‐discharge capacity loss in working Li–S batteries, simultaneously.