The amphiphilic block copolymer formed by a hydrophobic body of polystyrene and a hydrophilic head of poly[9,9-di(2-(2-tetrahydropyranyl-oxy)hexyl)fluorene-alt-9,9-dioctylflu orene] was synthesized, and its solution was used to create thin films with ordered pattern of holes, by means of the breath figure technique. These porous films, after a thermal treatment, were found to show ordered aggregates of the pi-conjugated blocks in the place of the cavities. This is probably due to a preorganization of the two different blocks of the copolymer occurring during the breath figure formation, which is driven by the condensation of water microdroplets on the polymer solution, and to a following phase segregation occurring during the thermal annealing. This approach is a promising tool to be employed for the organization of organic materials at the micro and nanoscale.