Hollow energetic microspheres have attracted great attention in the field of materials due to their wide application potential. However, scalable, simple, and low-cost production methods have not been achieved yet. In this study, using nitrocellulose (NC) as a binder, hollow and porous hollow CL-20 microspheres were prepared by the assist of microjet droplet technology. The effects of receiving liquid temperature, solution concentration, and solvent type on the morphology, particle size, shell thickness, and pore size of the CL-20 microspheres were systematically investigated. Furthermore, the influences of shell thickness and pore size on the dispersibility, crystal structure, thermal decomposition, mechanical sensitivity, and combustion behavior of CL-20 microspheres were further studied. The results showed that precise control over the shell thickness and pore size of CL-20 microspheres could be achieved by adjusting the process parameters. Compared to raw CL-20, the CL-20 microspheres exhibited excellent dispersibility and improved thermal and safety performance (raw CL-20 vs CL-20 microspheres, 40.3° vs 27.1° ∼ 29.1°; 240.4℃ vs 241.1 ∼ 246.2℃; 2 J vs 25 ∼ 32.5 J). Ignition experiments demonstrated that the hollow and porous hollow structures significantly enhanced the combustion flame of CL-20, shortened the burning time, and thereby improved energy release efficiency. This preparation method is simple and efficient, providing a new approach for the fabrication of multi-structured hollow energetic microspheres.