Hollow structures have great potential in the field of energetic materials due to their excellent properties. In this study, nitrocellulose (NC) was used as a binder, and hollow-structured HNS/NC microspheres were prepared in the form of a suspension using the microjet droplet technology. The effects of spray velocity, suspension concentration, and receiving liquid temperature on the morphology, particle size, cavity structure, and pore size of the microspheres were systematically investigated. Subsequently, the effects of shell thickness and pore size on the dispersibility, specific surface area, crystal structure, thermal performance, mechanical sensitivity, and combustion performance of the microspheres were further studied. The results show that compared with the raw HNS, the hollow HNS/NC microspheres have good dispersibility, while retaining the crystal structure and chemical structure of the raw HNS, and have a lower activation energy, which is expected to achieve a rapid energy release reaction. In addition, compared with the solid HNS/NC microspheres, the hollow HNS/NC microspheres have a higher specific surface area (19.658 m2·g−1 vs 31.335 m2·g−1) and better safety performance (6 J vs 50 J). The ignition experiment results show that the hollow structure significantly enhances the combustion performance of HNS (305 ms vs 92 ms), improving the energy release efficiency. This preparation method is simple, efficient, and easy to scale up, providing a more universal and environmentally-friendly technical approach for the multi-structural design of energetic microspheres.