The highly porous structures with porosities up to 95 %, low densities (< 0.1 g / cm3) and surface areas exceeding 500 m2/g are properties that distinguish our semiconducting π-conjugated polyelectrolyte (CPE) foams. Combination of such 3D-interconnected macroporous morphology and the photoactive π-electron backbone hold a great promise in the semiconductor-mediated heterogeneous photocatalysis.