Hierarchical nanoarchitectures constructed by MoO2 nanocrystal-functionalized graphene were fabricated through an in situ reduction process. As an anode, even at a 10C (0.1 h per half cycle) charging–discharging rate, the reversible capacity is much higher than the theoretical capacity of graphite. Thus, rapid charging–discharging of the anodes is achieved by the nanoarchitectures.