It is very important to develop ideal electrocatalysts to accelerate the sulfur redox kinetics in both the discharging and charging processes for high-performance lithium−sulfur batteries. Herein, defect-rich cation-doped V 2 O 5 yolk−shell microspheres are reported as a catalytic host of sulfur. The doping of W or Mo cations induces no impurities, broadens the lattice spacing of V 2 O 5 , and enriches the oxygen vacancy defects. Thus, the doped V 2 O 5 host affords sufficient active sites for chemically anchoring polysulfides and promising catalytic effect on the mutual conversion between different sulfur intermediates. As a result, the S/W−V 2 O 5 cathode delivers a discharging capacity of 1143.3 mA g −1 at an initial rate of 0.3 C and 681.8 mA g −1 at 5 C. Even under a sulfur loading of up to 5.5 mg cm −2 and a minimal electrolyte/sulfur ratio of 6 μL mg −1 , the S/W−V 2 O 5 cathode could still achieve good sulfur utilization and dependable cycle stability. Thus, this work offers an electrocatalytic host based on the cation doping strategy to greatly enhance the sulfur redox kinetics for high-performance Li−S batteries.