Self-assembled hierarchical MoO(2)/graphene nanoarchitectures have been fabricated on a large scale through a facile solution-phase process and subsequent reduction of the Mo-precursor/graphene composite. The as-formed MoO(2)/graphene nanohybrid as an anode material for lithium-ion batteries exhibits not only a highly reversible capacity but also an excellent cycling performance as well as good rate capability. Results show that the hierarchical rods made of primary MoO(2) nanocrystals are uniformly encapsulated within the graphene sheets. The synergistic effect of the hierarchical nanoarchitecture and the conducting graphene support may contribute to the enhanced electrochemical performances of the hybrid MoO(2)/graphene electrode. This work presents a facile synthetic strategy that is potentially competitive for scaling-up industrial production. Besides, the MoO(2)/graphene hybrids with a well-defined hierarchical topology not only provide flexible building blocks for advanced functional devices, but are also ideal candidates for studying their nanoarchitecture-dependent performances in catalytic and electronic applications.