Bicontinuous sugar-based microemulsions, containing up to 80 wt % of liquid divinylbenzene monomer relative to sugar, can be dehydrated to the solid glass state without phase separation. Photopolymerization of the liquid divinylbenzene present within the interstices of these solid microemulsion glass templates at temperatures below the onset glass transition of the sugar template proceeds with no phase separation. Comparison of the small angle scattering spectra of the microemulsion glasses before and after polymerization show almost no change in microstructure. Following polymerization, the bicontinuous structure of these microemulsion glasses permits straightforward and rapid dissolution of the sugar template to yield polydivinylbenzene membranes with similar to 25 nm pores.