Hollow reduced graphene oxide (RGO) microspheres are successfully synthesized in large quantities through spray-drying suspension of graphene oxide (GO) nanosheets and subsequent carbothermal reduction. With this new procedure, blighted-microspherical GO precursor is synthesized through the process of spray drying, afterwards the GO precursor is subsequently calcined at 800°C for 5h to obtain hollow RGO microspheres. A series of analyses, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR) are performed to characterize the structure and morphology of intermediates and as-obtained product. The as-obtained hollow RGO microspheres provide a high specific surface area (175.5 m2 g−1) and excellent electronic conductivity (6.3 S cm−1), and facilitated high electrochemical performance as anode material for Li-ion batteries (LIBs). Compared with the RGO nanosheets, the as-obtained hollow RGO microspheres exhibit superior specific capacity and outstanding cyclability. In addition, this spray drying and carbothermal reduction (SDCTR) method provided a facile route to prepare hollow RGO microspheres in large quantities.