The advantages of high energy density and low cost make lithium–sulfur batteries one of the most promising candidates for next-generation energy storage systems. However, the electrical insulativity of sulfur and the serious shuttle effect of lithium polysulfides (LiPSs) still impedes its further development. In this regard, a uniform hollow mesoporous Ni(OH)₂@CNT microsphere was developed to address these issues. The SEM images show the Ni(OH)₂ delivers an average size of about 5 μm, which is composed of nanosheets. The designed Ni(OH)₂@CNT contains transition metal cations and interlayer anions, featuring the unique 3D spheroidal flower structure, decent porosity, and large surface area, which is highly conducive to conversion systems and electrochemical energy storage. As a result, the as-fabricated Li-S battery delivers the reversible capacity of 652 mAh g⁻¹ after 400 cycles, demonstrating excellent capacity retention with a low average capacity loss of only 0.081% per cycle at 1 C. This work has shown that the Ni(OH)₂@CNT sulfur host prepared by hydrothermal embraces delivers strong physical absorption as well as chemical affinity.