A three-dimensionally ordered macroporous ZnO (3DOM ZnO) framework was synthesized by a template method to serve as a sulfur host for lithium–sulfur batteries. The unique 3DOM structure along with an increased active surface area promotes faster and better electrolyte penetration accelerating ion/mass transfer. Moreover, ZnO as a polar metal oxide has a strong adsorption capacity for polysulfides, which makes the 3DOM ZnO framework an ideal immobilization agent and catalyst to inhibit the polysulfides shuttle effect and promote the redox reactions kinetics. As a result of the stated advantages, the S/3DOM ZnO composite delivered a high initial capacity of 1110 mAh g−1 and maintained a capacity of 991 mAh g−1 after 100 cycles at 0.2 C as a cathode in a lithium–sulfur battery. Even at a high C-rate of 3 C, the S/3DOM ZnO composite still provided a high capacity of 651 mAh g−1, as well as a high areal capacity (4.47 mAh cm−2) under high loading (5 mg cm−2).