With the rapid development of ultra large scale integrated circuits, low stress, low thermal expansion, low dielectric constant, and low temperature curable (<250 °C) polyimides (PIs) with excellent mechanical, thermal properties are required. Unfortunately, high curing temperatures above 300 °C and limited dielectric property still remain to be solved. Herein, a new type of aminopropyl isobutyl polysilsesquioxane (POSS) with single vertex activity is introduced by in situ polymerization resulting in the PI‐POSS nanocomposites which exhibit a low dielectric constant (κ ≤ 2.6). Furthermore, low‐temperature curing at 200 °C (99.4% imidization) under the catalysis of quinoline is also achieved. The as‐prepared PI‐POSS nanocomposites also show excellent mechanical properties of which the tensile strength can reach up to 148 MPa and the elongation at break achieves 98%. Moreover, the temperature of weight loss 5% is as high as 550 °C and the glass transition temperature can also reach 349 °C. The as‐prepared PI‐POSS nanocomposites prove excellent electrical performance and mechanical properties, showing a huge market prospect of 5G chip packaging and millimeter wave antenna in the future.