Abstract: Charge-splitting networks, optoelectronic devices, methods for making optoelectronic devices, power generation systems utilizing such devices and method for making charge-splitting networks are disclosed. An optoelectronic device may include a porous nano-architected (e.g., surfactant-templated) film having interconnected pores that are accessible from both the underlying and overlying layers. A pore-filling material substantially fills the pores. The interconnected pores have diameters of about 1-100 nm and are distributed in a substantially uniform fashion with neighboring pores separated by a distance of about 1-100 nm. The nano-architected porous film and the pore-filling material have complementary charge-transfer properties with respect to each other, i.e., one is an electron-acceptor and the other is a hole-acceptor. The nano-architected porous, film may be formed on a substrate by a surfactant temptation technique such as evaporation-induced self-assembly.