Porous Si/C/reduced graphene oxide (Si/C/rGO) microspheres have been prepared by the spray drying and subsequent carbonization process using the polyvinyl alcohol (PVA) as cross-linking agent. PVA plays an important role in the spray drying process. The designed micrometer-size reduced graphene oxide wrapped Si/C ball structure offers a buffer space for the volume change of Si during the charge-discharge process. Double carbon layers can effectively protect the Si core and improve the cycling stability of the electrode. The fabricated Si/C/rGO microspheres as anode for lithium ion batteries exhibit a high reversible capacity of 928mAhg−1 after 70cycles at a current density of 100mAg−1, good rate capability and cycling stability.