In this study, reduced graphene oxide/polyimide (r-GO/PI) composite films, which showed significant enhancement in their electrical conductivity, were successfully fabricated. GO was prepared from graphite using a modified Hummers method. The GO was used as a nanofiller material for the preparation of r-GO/PI composites by in-situ polymerization. An addition of 20 wt% of GO led to a significant decrease in the volume resistivity of composite films by less than nine orders of magnitude compared to that of pure PI films due to the electrical percolation networks of reduced GO created during imidization within the films. A tensile test indicated that the Young’s modulus of the r-GO/PI composite film containing 20 wt% GO increased drastically from 2.3 GPa to 4.4 GPa, which was an improvement of approximately 84% compared to that of pure PI film. In addition, the corresponding tensile strength was found to have decreased only by 12%, from 113 MPa to 99 MPa.