We describe a multibeam interference lithography for creating 3D polymeric porous structures. The coating of a TiO(2) shell and subsequent removal of the template produce holographically defined TiO(2) (h-TiO(2)) electrodes. We analyze the morphological features of the h-TiO(2) electrodes and consider their applicability to dye-sensitized solar cells (DSSCs). Specifically, the performance of the h-TiO(2) electrode was evaluated by comparison with a macroporous TiO(2) electrode produced from colloidal crystals. The h-TiO(2) structure possesses a larger specific area than the inverted colloidal crystals because of a bicontinuous air network with the TiO(2) shell. Consequently, the h-TiO(2) electrode can produce a 30% higher photogenerated electron current.