Multi-layer graphene sheets have been synthesized by a time-efficient microwave autoclave method and used to form composites in situ with single-walled carbon nanotubes. The application of these composites as flexible free-standing film electrodes was then investigated. According to the transmission electron microscopy and X-ray diffraction characterizations, the average d-spacing of the graphene-single-walled carbon nanotube composites was 0.41 nm, which was obviously larger than that of the as-prepared pure graphene (0.36 nm). The reversible Li-cycling properties of the free-standing films have been evaluated by galvanostatic discharge-charge cycling and electrochemical impedance spectroscopy. Results showed that the free-standing composite film with 70 wt% graphene exhibited the lowest charge transfer resistance and the highest charge capacity of about 303 mAh g-1 after 50 cycles, without any noticeable fading.