Hierarchical hollow microspheres with nickel sulfide (NiS) nanorods as the in situ formed building blocks have been fabricated via a novel precursor hydrothermal method in alkaline solution of Na₂S. In addition, hierarchical hollow microspheres with NiS nanoparticles as the in situ formed building blocks have also been successfully controlled-synthesized through the adjustment of experimental parameters. The NiS powders have been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction and high-resolution transmission electron microscopy. The reported controlled experiments allow us to propose the formation mechanism of nanorod-based NiS hierarchical hollow spheres, which involves sulfuration of Ni(OH)₂ precursors and their sequential Ostwald ripening process. When the two kinds of NiS hierarchical hollow spheres prepared herein are used as cathode materials for lithium-ion batteries, nanorod-based hierarchical hollow microspheres exhibit enhanced electrochemical properties as compared with nanoparticle-based hierarchical hollow microspheres. Electrochemical measurements have also shown that the initial discharge capacity of nanorod-based hierarchical hollow microspheres is 587.8 mAh·g⁻¹, which is close to the theoretical capacity of NiS (590 mAh·g⁻¹). The results described in the present work may open up another way for the design of novel nanostructured materials for various applications.