The fabrication of flexible freestanding electrodes with superior electrochemical performance is challenging now in consumer electronics miniaturization. Herein, we demonstrate a simple and scalable synthesis of hollow silicon nanosheets, which then hybridizes with rGO into flexible films by layer-by-layer assembly process. The resulting Si/rGO films, when applied as a free-standing LIBs anode, exhibit a high reversible specific capacity of 904 mAh g−1 at 200 mA g−1 (about 2 times higher than theoretical value of graphite anode), and meanwhile maintain a long cycle life (650 mAh g−1 after 150 cycles). In addition, a flexible full battery has also been assembled based on the flexible film as an anode and the commercial LiCoO2 as a cathode, which impressively delivers a high specific capacity of 700 and 613 mAh g−1 at 50 mA g−1 after 15 cycles in flat and bent state, respectively. Such intriguing electrochemical performances can be mainly attributed to the two-dimensional hollow nanostructure of silicon and their strong synergistic effect with rGO. It is reckoned that our Si/rGO films are a promising anode for advanced flexible LIBs.