A general strategy for constructing graphene-based nanocomposites is achieved by emulsion-based bottom-up self-assembly of hydrophobic nanocrystals (NCs) to positively charged colloidal spheres, followed by the electrostatic assembly of NC colloidal spheres with negatively charged graphene oxide in an acidulous aqueous solution. With a simple heat treatment, 3D mesoporous NC spheres/graphene composites are obtained. TiO2/graphene composites typically exhibit a better rate capability and cycle performance than do the corresponding isolated TiO2 spheres.