The aim of this work is to introduce a high performance cathode for magnesium-ion batteries. TiO2/reduced graphene oxide (rGO) composites were mixed in ball mill. The samples are characterized using XRD and SEM. The spex-milled composites exhibit better electrochemical performance with higher reversible capacity and excellent cyclability. The excellent electrochemical performance of TiO2/rGO composites is due to their unique structures, which intimately combine the conductive graphene nanosheets network with TiO2 nanoparticles and possess the characteristic parallel channels running along the [010] orientation, which allow easy Mg2+ transport. It was found that layered TiO2 and rGO nanosheets in the composite interlace with each other to form novel sandwich-structured microspheres, which exhibit preferable electrochemical performance in rechargeable Mg batteries.