<p>Polyimide (PI) aerogels are at the forefront of heat insulation applications. However, their relatively limited mechanical strength and thermal insulation performance constrain their broader application. This study presents an innovative strategy for preparing PI/ZrO₂ composite aerogels with a double-cross-linked network structure. The embedding of ZrO₂ nanoparticles into the PI aerogel matrix was enabled by the formation of hydrogen bonds and Zr—O bonds, thus leading to the creation of an ordered, layered network architecture. The introduction of ZrO₂ nanoparticles caused a reduction in the thermal conductivity of the PI/ZrO₂ composite aerogel from 0.0367 W·m⁻¹·K⁻¹ to 0.0305 W·m⁻¹·K⁻¹. Meanwhile, it significantly increased the compressive strength of the PI/ZrO₂ composite aerogel. When the ZrO₂ content is 2%, the mechanical strength increases from 0.67 MPa to 1.43 MPa. At 800 °C, the residual mass of the PI/ZrO₂-5% aerogel exceeded that of the PI aerogel by 2.3%. These enhancements can be attributed to the cross-linked network triggered by the ZrO₂ nanoparticles. Owing to its low thermal conductivity and high-temperature tolerance, ZrO₂ remarkably improved the thermal insulation and thermal stability of the aerogel. To assess the feasibility of industrial-scale application of the PI/ZrO₂ composite aerogel, a series of pilot-scale amplification experiments were conducted. These results confirm the stability and reproducibility of the synthesis process. The PI/ZrO₂ composite aerogel exhibited considerable potential for a wide range of applications across diverse fields.</p>