The feasible control of the microstructures of porous polymeric materials has been studied by polymerization of monomer(s) containing bicontinuous microemulsions. Microstructures of the resulting polymeric materials can be varied by incorporating a different weight ratio of a nonpolymerizable surfactant, sodium dodecyl sulfate, and a polymerizable surfactant, sodium 11-(N-ethylacrylamido)undecanoate. The pore sizes in the materials are the water-filled spaces between the incompletely coalesced spherical aggregates, and they are regulated by the size of these aggregates. The morphology of the polymeric materials was examined by field emission scanning electron microscopy. The thermal analysis of the polymeric materials was also investigated, and a possible mechanism for microstructural modification is discussed.