In this article, the effects of coupling agent, silica particle size, and particle shape on the mechanical properties of polyimide (PI) were studied by molecular dynamics (MD) simulations, and the effect of SiO 2 surface treated with coupling agent on the mechanical properties of PI was investigated by experiment. At the same doping volume fraction (5%), the simulation results show that the surface interaction energy between the matrix and particle gradually increases with the radius of the embedded nanoparticles. Meanwhile, the interface interaction energy and mechanical properties of the sphere-type were significantly higher than the ones of other shaped nanoparticles. Moreover, the simulations were compared with the experimental results; atomic force microscopy and scanning electron microscopy images can verify that after being treated with coupling agent, interface interaction between nanosilica and PI enhances quite a little. The mechanical experimental results show that the tensile strength and elasticity modulus of pure PI, unbonded (UB) PI/SiO 2 , and bonded PI/SiO 2 films are 34.47 and 1.13, 36.46 and 1.32, and 66.20 MPa and 1.72 GPa, respectively. It is indicated that the coupling agent plays a crucial role in nanocomposites.