Polymeric honeycomb microporous films were prepared from fluorinated diblock copolymers, poly(tert-butyl acrylate)-b-poly(2-[(perfluorononenyl)oxy]ethyl methacrylate) (PtBA-b-PFNEMAs), and four other commercial polymers, including polystyrene (PS), polycarbonate (PC), polylactic acid (PLA), and polymethylmethacrylate (PMMA) via breath figures method. The as-formed fluorinated diblock copolymer micelles in chloroform were not only utilized to stabilize the templated water droplets in bulk, but also introduced as the water droplets stabilizer in other polymeric materials. Our strategy was successfully achieved, as the micropores were decorated with the fluorinated diblock copolymer as directly shown in the SEM images and FT-IR/ATR-FTIR. Polymer concentration and the solution casting volume effects were checked to tune the sizes of the micropores in diblock copolymer films. The ratio of the added fluorinated diblock copolymer as a novel factor to tune the sizes of the micropores was also investigated.