3D, fully interconnected, ultraporous polymer materials are produced by assembling polyelectrolyte and protein molecular layers onto a porous co-continuous polymer-blend template that is subsequently removed by selective solvent extraction (see figure). These structures possess highly controlled, fully continuous microstructures with void fractions up to 99.6 %, internal surface areas per unit volume up to 2.3 mu m(-1), and specific surface areas up to 140 m(2) g(-1).