MgH 2 nanoparticles (NPs) uniformly anchored on graphene (GR) are fabricated based on a bottom-up self-assembly strategy as anode materials for lithium-ion batteries (LIBs). Monodisperse MgH 2 NPs with an average particle size of ∼13.8 nm are self-assembled on the flexible GR, forming interleaved MgH 2 /GR (GMH) composite architectures. Such nanoarchitecture could effectively constrain the aggregation of active materials, buffer the strain of volume changes, and facilitate the electron/lithium ion transfer of the whole electrode, leading to a significant enhancement of the lithium storage capacity of the GMH composite. Furthermore, the performances of GMH composite as anode materials for LIBs are enabled largely through robust interfacial interactions with poly(methyl methacrylate) (PMMA) binder, which plays multifunctional roles in forming a favorable solid-electrolyte interphase (SEI) film, alleviating the volume expansion and detachment of active materials, and maintaining the structural integrity of the whole electrode. As a result, these synergistic effects endow the obtained GMH composite with a significantly enhanced reversible capacity and cyclability as well as a good rate capability. The GMH composite with 50 wt % MgH 2 delivers a high reversible capacity of 946 mA h g -1 at 100 mA g -1 after 100 cycles and a capacity of 395 mAh g -1 at a high current density of 2000 mA g -1 after 1000 cycles.