Ladder-like polysilsesquioxanes (LPSQs) with different amino contents have been synthesized by controlling of the dosage of Pd/C catalyst. The concentration and activity of amino groups were investigated by Fourier transform infrared spectroscopy. Polyimide (PI)/LPSQ hybrid films have been prepared by incorporating of the obtained LPSQs with different amino contents into PI matrix, respectively. The interfacial interactions between PI matrix and LPSQ were studied with scanning electron microscopy and X-ray photoelectron spectroscopy, meanwhile the thermal and mechanical properties of the hybrid films were studied using dynamic mechanical analysis and tensile tests. The results indicate that the functionality of LPSQ has great effects on the interfacial interactions and the properties of hybrid films. With the increase of amino content, both the interfacial interactions and the cross-linking density of hybrids enhanced, which results in the decline of surface silicon concentration, increase of Young’s modulus and drop of elongation at break. Excessive amino content makes the hybrid films brittle and leads to incomplete imidization. Ladder-like polysilsesquioxanes (LPSQs) with different amino contents have been synthesized by controlling the dosage of Pd / C catalyst. The concentration and activity of amino groups were investigated by Fourier transform infrared spectroscopy. Polyimide (PI) / LPSQ hybrid films have been prepared by incorporating the obtained LPSQs with different amino contents into PI matrix, respectively. respectively. The interfacial interactions between PI matrix and LPSQ were studied with scanning electron microscopy and X-ray photoelectron spectroscopy, meanwhile the thermal and mechanical properties of the hybrid films were studied using dynamic mechanical analysis and tensile tests. The results that that functionality of LPSQ has great effects on the interfacial interactions and the properties of hybrid films. With the increase of amino content, both the interfacial interactions and the cross-linking density of hybrids enhanced , which results in the decline of surface silicon concentration, incr ease of Young’s modulus and drop of elongation at break. Excessive amino content makes the hybrid films brittle and leads to incomplete imidization.