A quaternary hierarchical nanocomposite, rGO-Fe3O4-SnO2-C, is rationally designed and synthesized via layer-by-layer constructions of reduced graphene oxide (rGO) flexible films, Fe3O4 nanoparticles, SnO2 nanoparticles and an omnidirectional amorphous carbon layer. SEM and TEM observations show that the Fe3O4 and SnO2 nanoparticles are uniformly dispersed on the rGO nanosheets and fully encapsulated by the outmost carbon layers, forming a sandwich-like buffering structure for excellent dimensional integrity. Furthermore, nanopores with an average size of 5.8nm are fabricated within the quaternary hybrid nanosheets via a layer-by-layer packing of Fe3O4 and SnO2 nanoparticles, which possess the different shapes and sizes. Galvanostatic charge/discharge measurements demonstrate that rGO-Fe3O4-SnO2-C exhibits a reversible capacity of 868.6mAhg−1 after 100 cycles at a current density of 200mAg−1. Even at a current density of 2.0Ag−1, it can be stably operated during the discharge/charge processes and deliver a reversible capacity of 414.7mAhg−1. The excellent electrochemical properties of rGO-Fe3O4-SnO2-C can be attributed to the microstructural stability of the hybrid and the synergistic effects of the components inside the nanosheets.