Due to high theoretical capacity, lithium sulfur (Li–S) batteries are regarded as aussichtsreich batteries for future energy storage devices. Several factors, such as low usage effectiveness of sulfur and “shuttle effect” of polysulfides, restrain the development of Li–S batteries. Porous sulfur carriers have been developed to remit these shortcomings to some extent. In this paper, a simple strategy is reported to prepare porous Ni3S2 hollow microspheres as sulfur hosts for Li–S batteries by an easy hydrothermal and calcination method. The as-fabricated Ni3S2/S cathodes present excellent cycling performance (959.7 mA h g−1 at 0.1 C after 100 cycles) as well as good rate property and cyclability (557.5 mA h g−1 at 1 C after 400 cycles). Such excellent energy storage properties can be ascribed to the unique hollow microsphere structure with high specific surface area, which is conducive to the capture of polysulfides during cycling. The study also provides a simple route to develop transition metal sulfide with hollow structures as superior sulfur hosts which may promote the development of various hollow structures for Li–S batteries application. Display omitted •Porous Ni3S2 hollow microspheres are prepared as sulfur hosts for Li–S batteries.•Ni3S2/S exhibit good electrochemical performance as Li–S battery cathodes.•Porous Ni3S2 hollow structure is conducive to capture polysulfide.•Large specific surface area of electrode can well adapt volume change of S.