The ignition strategy of energetic materials using low-energy near-infrared (NIR) laser has garnered significant attention due to its enhanced safety and reliability. This study explores the use of a relatively photosensitive but mechanical insensitive energetic material, DATNBI, to facilitate the self-assembly of nano-CL-20 crystals into polycrystalline particles though solvothermal induction, yielding a rough structure conducive to NIR laser ignition. The findings demonstrate that by adjusting the content of DATNBI, it is possible to achieve micro-nano controllable spherical CL-20/DATNBI (C/D) particles, with CL-20 as the primary component and DATNBI as the auxiliary component. The incorporation of DATNBI and the rough surface structure enhance the light absorption of C/D particles in the NIR band. Additionally, the unique synergistic effect between CL-20 and DATNBI during thermal decomposition further promotes NIR laser ignition. As expected, the C/D particles achieved self-sustained combustion and exhibited excellent combustion performance under a 1064 nm laser, which is challenging to be achieved with raw CL-20 or raw DATNBI. Furthermore, the relatively insensitive DATNBI and spherical structure reduced the impact sensitivity of the C/D particles. This multifunctional material strategy, integrating energy, safety environment-friendliness, and laser ignition performance, offers a novel approach for laser ignition of energetic materials.