Polymerization of single-phase microemulsions produces microporous solid materials. The surface morphology of the polymer solids, after drying, was examined using scanning electron microscopy (SEM). The microstructure of the precursor microemulsion is preserved to a considerable extent on polymerization, at least in a qualitative sense. The microstructure within the bulk of the polymers was characterized by the shape of drying-rate curves determined using thermogravimetric analysis. The results reveal that bicontinuous microemulsions yield polymers with an open-cell structure whereas microemulsions with less than 20% water content form closed-cell structures. The pore size distribution (PSD) of the aspolymerized solids was obtained using a high-resolution low-temperature DSC technique. A comparison of the SEM pictures with the results of the PSD shows that the mode of drying affects the porosity and that the pores increase in size during drying.