Abstract Lithium/sulfur (Li/S) battery has been regarded as promising candidate for next-generation energy storage systems due to the high energy density. The big obstacle to realize the practical application of Li/S battery is to synchronously accelerate the redox kinetics and restrain the dissolution of polysulfides into the electrolyte. On this account, ZnS nanotubes with abundant sulfur vacancies (ZnS1−x) are constructed and deposited onto a freestanding carbon cloth electrode for Li/S batteries. The combination of architectural and sulfur-vacancy engineering regulates the electronic structure of ZnS as well as its interactions with active sulfur, thus by facilitates ion/electron transfer, immobilizes lithium polysulfide, and accelerates sulfur reaction kinetics. As a consequence, a capacity of 1043 mAh g−1 is obtained under a low current density of 0.2 C, as well as a capacity retention of 524 mAh g−1 over 500 cycles at 1 C. This work presents a convenient and effective material design strategy to improve the performance of Li/S batteries and promote the practical process.