In this work, we introduced a facile approach for preparing hollow graphene oxide spheres (HGOSs). By electrostatic self-assembly polystyrene (PS)/graphene oxide (GO), core/shell microspheres were synthesized. After removal of the sacrificial PS colloidal spheres by toluene solution treatment, HGOSs were prepared successfully. Based on the DLVO theory, van der Waals force and electric double layer repulsion were proposed to quantitatively analyze the self-assembly of the composite structure. The theoretical formulation for the resultant interaction force F versus separation between the surfaces d showed a significant low energy barrier for the aggregation of the GO and PS, which predicted the favorable HGOSs formation.