Herein, we aim to develop a facile method for the fabrication of mesoporous polystyrene (PS) films with controlled porosity and pore size by solvent annealing. A PS polymer film is solvent-annealed using N,N-dimethyl formamide (DMF) vapor for the development of phase separation, followed by rapidly cooling to the preset cryogenic temperature. Subsequently, a nonsolvent (methanol) is introduced to extract the crystalline DMF from the DMF-swollen PS, giving mesoporous PS with a network structure after the removal of DMF. The porosity of the mesoporous PS films can be controlled by the degree of swelling. Most interestingly, the phase separation between PS and DMF at the thin-film state under solvent annealing can be regulated by the annealing time through the spinodal decomposition, giving the development of nanonetwork structure with controlled structural features (i.e., framework size and interframework spacing) at invariant porosity. Consequently, after the removal of DMF, mesoporous PS films with controlled porosity and pore size can be obtained and then used as a template for the fabrication of a variety of nanoporous inorganics by templated syntheses, such as nanoporous SiO2, TiO2, and Ni, providing a cost-effective way to fabricate a range of nanoporous materials with controlled porosity and pore size as well as large specific surface area for aimed applications.