Graphene-MnO composite and hollow-structured MnO powders are prepared by a simple one-pot spray pyrolysis process. The graphene content in the graphene-MnO composite powder is estimated to be 10wt.%. The fine MnO crystals of size several tens of nanometers are uniformly distributed all over the graphene. The BET specific surface areas of the graphene-MnO composite and hollow-structured MnO powders are found to be 20 and 5 m2 g−1, respectively. The graphene-MnO composite powders have high initial discharge and charge capacities of 1207 and 849mA h g−1, respectively, at a current density of 500mAg−1. The initial discharge and charge capacities of the hollow-structured MnO powders are 1004 and 673mA h g−1, respectively. The discharge capacities of the graphene-MnO composite and hollow-structured MnO powders for the 130th cycle are 1313 and 701mA h g−1, respectively.