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In this article, oxygen doped boron nitride (OBNNS) was selected and introduced into PI to form OBNNS/PI composite films. The thermal, electrical, optical and mechanical properties of the OBNNS/PI composite films were all improved compared to pure PI. Our experimental results shown that the synthesized OBNNS/PI composite with a low OBNNS content (0.25 wt%) have thermal conductivity of 0.291 W·m−1·K−1, tensile strength of 127.1 MPa, elongation at break of 13.3%, and corona resistant life of 9.50 h, all were significantly enhanced compared with that of a pure PI film. This can be attributed the homogeneous and ordered dispersion of OBNNS in PI matrix. The successful preparation of the OBNNS/PI composites will pave a way for the development of multifunctional polyimide-based composites for applications. Keywords: Polyimide, Boron nitride, Multifunctional, Application