Highly ordered hexagonal patterns of a commercially available polystyrene (PS) thin film are successfully fabricated via an improved phase separation method. A mixture of chloroform (ChL) and methanol (MeOH), which is used as a solvent/ non-solvent pair, exhibits strong potential and high sensitivity for producing highly ordered honeycomb films with mono-dispersed and tunable pore sizes. It is demonstrated that a ChL/MeOH volume ratio of 90/10 is the optimal ratio for fabricating the highest quality of honeycomb films. The patterned film is further modified to enhance the solvent resistance as well as thermal stability through crosslinking the PS via deep UV irradiation. The convergence of cost effective, large-scale production and the robustness of highly ordered honeycomb film enables new applications for commercialization in the fields of microporous films and outdoor applications. (C) 2015 Elsevier Ltd. All rights reserved.