MnO2/reduced graphene oxide (rGO) nanocomposites were synthesized via a simple solution method at room temperature for use in Li-ion batteries. Owing to the mesoporous features as well as the high electrical conductivity of rGO, the overall electronic and ionic conductivities of the nanocomposite were increased, resulting in improved electrochemical properties in terms of specific capacity, rate capability, and cyclability. In particular, as-prepared nanocomposites showed 222 and 115 mAh g−1 at a current density of as high as 5 and 10 A g−1, and the specific capacitance was well maintained after 400 cycles. In addition, MnO2, via composite formation with rGO, permitted the additional conversion reaction between MnO and Mn3O4, resulting in the reduction of the initial irreversible capacity despite the high first discharge capacity caused by the large specific surface area.