In this work, we reported a simple method to fabricate novel free-standing stiff carbon-based composite films with excellent mechanical properties and superhydrophobic behaviors. The free-standing stiff carbon composite films based on reduced graphene oxide/glassy carbon (rGO/GC) were prepared by the combination of in-situ polymerization and carbonization process. The obtained composite films exhibited excellent mechanical properties by the addition of rGO nanosheets. It was found that incorporating 0.5 wt.% of rGO sheets in GC precursors resulted in enhancements of 99% in strength (202.6 MPa) and 184% in modulus (33.8 GPa), respectively. More interestingly, carbon nanoarrays were uniformly grown on the surface of composite films by the incorporation of rGO sheets. Superhydrophobic surfaces of carbon films were subsequently formed through functionalizing carbon nanoarrays with Trichloro(1H, 1H, 2H, 2H-perfluorodecyl)silane. Contact angle (CA) analysis suggested that superhydrophobic surfaces with a CA as high as 155° could be formed through optimizing the fabrication process.