The possibility of preparing microcapsules composed of expanded polystyrene (EPS) in a (W/O)/W' multiple emulsion system was investigated. Glycerol aqueous solution was employed to control the inner structure of microcapsules, (R)-(+)-limonene solution of EPS was used as the dispersed phase, and ethylene glycol solution of polyvinyl alcohol (PVA) was used as the continuous phase. It was found that the specific surface area of microcapsules increased with the concentration and the loading of glycerol aqueous solution, and also increased with the concentration of PVA in the continuous phase.