Polymeric materials have many applications in multiple industries. In this paper, silicon nitride nanoparticles (Si₃N₄) were incorporated into a polyimide (PI) matrix to obtain composite films via the in situ polymerization method. The Si₃N₄ nanoparticles were consistently scattered in the composites, and the thickness of PI/Si₃N₄ films was around 50 µm. The effects of nanoparticle content on the dielectric constant, loss tangent and breakdown strength were simultaneously studied. A 3 wt.% doped PI/Si₃N₄ film revealled excellent dielectric properties, a dielectric constant (ε) of 3.62, a dielectric loss tangent (tanδ) of 0.038, and a breakdown strength of 237.42 MV/m. The addition of Si₃N₄ formed an interface layer inside PI, resulting in a large amount of space charge polarization in the electric field. The space charge of materials from the microscopic point of view was analyzed. The results show that there are trapenergy levels in the composites, which can be used as a composite carrier center and transport channel, effectively improving the performance of a small amount of nanoparticles film.