Polyimide belongs to the class of high performance polymers containing imide functionalities in the backbone. Polyimide has wide ranging properties of optical transparency, heat stability, mechanical strength, dimensional stability, thermal conductivity, dielectric properties, etc. Fullerene is a zero dimensional hollow symmetrical nanocarbon, frequently employed as nanofiller in the polymers. Fullerene has been reinforced in the polyimide films to further augment the exclusive features and performance. This state-of-the-art review basically emphases the fundamentals, structure, properties, and applications of polyimide films, especially the films reinforced with fullerene nanofiller. The polyimide/fullerene nanocomposite films have been prepared using facile routes such as solution casting, spin casting, in situ method, and other film forming methods. Fullerene nanofiller has been filled in numerous designed polyimides. Number of experimental and theoretical studies have been performed on the high performance polymer/fullerene nanocomposite films. The structural diversity of the polymer/fullerene nanocomposite films and inimitable characteristics have led to significant applications in the optoelectronic devices, photodetectors, and sensors.