We report a new technique of creating a nanoporous polymeric nanostructure by photo-patterning emulsions generated from a formamide (polar phase) and an acrylate-monomer (nonpolar phase). Formamide is a highly polar solvent that forms well dispersed, non-aqueous emulsion droplets within the monomer-containing nonpolar phase before holographic patterning. Photochemically initiated polymerization of the nonpolar phase (acrylate monomer) forces the formation of ordered formamide emulsions defined by the holographic interference. Evaporation of the formamide from the ordered structure yields a periodic structure with high optical reflectivity and a wide reflection bandwidth. The average size and the size distribution of formamide droplets in the photopolymer fluid must be controlled to fabricate a periodic structure with high reflectivity. Furthermore, we found that the addition of sodium dioctyl sulfosuccinate (AOT) surfactant helps to stabilize the formamide emulsion which further facilitates the formation of the ordered nanopores with uniform size.