Highly ordered hexagonal arrays of isoporous films prepared from poly(9,9'-dihexylfluorene) and polystyrene-grafted silica nanoparticles (Si-graft-PS) are presented. These close-packed arrays were formed in areas of many square millimeters. The pore size varied from 3.6 to 8.5 microm, depending on the concentration of Si-graft-PS and the processing conditions. Solid-state photoluminescence resulted in a significant red shift of up to 30 nm in these films compared to that in conventional processing techniques. These differences are attributed to enhanced aggregation of the polymers caused by polymer-solvent interactions. These highly ordered polymer films may find use in microelectronic and biological and/or chemical sensor applications.