Flexible and free-standing MoS2/GS films are constructed for the first time based on a novel heat-induced formation process, during which self-generated gaseous species successfully trigger the formation of porous structure, without the assistance of any templates or spacers. Graphene forms an open porous network, with few-layered MoS2 uniformly grown on the surface of GS. The fascinating structure provides several attractive features as anode material, including efficient ion transport, high conductivity and good structure durability. When used as free-standing and binder-free electrodes for lithium-ion batteries, the optimized hybrid film with graphene content of 32% exhibits superior rate capability (994, 880, and 598mAhg−1 at 0.5, 1, and 5Ag−1, respectively) and outstanding cycling performance at high rates (retaining 100.6% of the initial capacity after 1000 cycles at 1000mAg−1). Importantly, the electrochemical reaction kinetics and interfacial behavior of the hybrid electrode are also in-depth investigated by EIS and morphological study. The work described here can be extended to prepare various porous graphene-based hybrid films, for the application in a broad range of LIBs, electrochemical capacitors, sensors, and catalysts.