Lithium–sulfur batteries, due to their various advantages such as their unique theoretical capacity, inexpensive, and environmental friendliness, have become one of the new‐generation energy storage systems. However, during the commercial development of lithium–sulfur batteries, they are limited by obstacles such as the volume expansion, shuttle effect, and low conductivity of S, which eventually lead to slow system reaction kinetics and poor cycling stability. Herein, heterostructured metal–organic framework‐derived Co3O4/TiO2hybrids have been designed. The hollow structure of the Co3O4is coupled with TiO2on the surface to form a heterojunction to construct an internal electric field, which can promote charge transfer and improve reaction kinetics. Meanwhile, Co3O4/TiO2has excellent trapping ability for lithium polysulfide, reducing the shuttle effect and alleviating volume expansion. As the cathode material, the initial discharge capacity of S@Co3O4/TiO2at 0.1C is 1152.7 mAh g−1. Meanwhile, it has an initial specific capacity of 657 mAh g−1at 1C, a capacity retention rate of 63.7% after 500 charge/discharge cycles, and an effective cycling stability with a decay rate of 0.072% in each cycle. This indicates that the construction of heterojunctions between materials has some enhancement on the performance of Li–S batteries. Herein, the hollow structure of Co3O4coupled with TiO2on the surface to form a heterojunction to build an internal electric field can promote charge transfer and improve the reaction kinetics as the cathode material, which has an initial specific capacity of 657 mAh g−1at 1C and a decay rate of 0.072% per cycle.