Miniaturization and integration of electronic components lead to increasing challenges of thermal management. Ultrathin materials with excellent thermal and flexibility are urgently required for portable electronic devices. In this study, the 1-pyrenemethanol (PyM) modified graphene oxide (GO) (GO-PyM) films were prepared in ethanol solution by an evaporation-induced assembly method. The PyM interacts with the GO sheets by hydrogen bonds and π-π interactions. The GO-PyM films were further graphitized at 3000 °C and roll compressed to fabricate the graphene films (GFs), by which, the PyM was transformed into nanosized graphite crystals (PNGCs). The PNGCs filled the voids between the graphene sheets of GFs and linked the graphene sheets, which enhanced the interaction between the graphene sheets, restricted the slippage of the graphene sheets under tension, increased the number of paths for electrons and phonons, and reduced the interface thermal resistance resulted from the existed voids. The resulting GFs showed excellent flexibility of a large elongation up to 14% and an elastic zone up to 3%, a tensile strength of 30.4 MPa, a thermal conductivity of 1316.32 W m-1 K-1, and an electrical conductivity of 6.48 × 105 S m-1. These integrated excellent properties of GFs will promote their applications in thermal management.