Emulsion polymerization of styrene was carried out using two kinds of alkyl polyoxyethylene ether sulfosuccinates as surfactant: disodium cetyl polyoxyethylene (25) ether sulfosuccinate (CPS) and octyl-phenol polyoxyethylene (10) ether sulfosuccinate (OPS). In experiments, the incorporation of CPS or OPS inside styrene droplets and polystyrene particles was clearly observed. Based on this phenomenon, multihollow polymer spheres are prepared in a one-step reaction and this strongly supports the proposed incorporation mechanism. CPS is more effective than OPS during the preparation of multiporous spheres. This difference between the two surfactants mainly contributes to the difference of the length of the EO (polyoxyethylene) group, which can determine the affinity among surfactant, styrene, and water molecules.