Hierarchical honeycomb patterns were manufactured with breath-figures self-assembly by drop-casting on the silicone oil-lubricated glass substrates. Silicone oil promoted spreading of the polymer solution. The process was carried out with industrial grade polystyrene and polystyrene with molecular mass M w = 35 , 000 g m o l . Both polymers gave rise to patterns, built of micro and nano-scaled pores. The typical diameter of the nanopores was established as 125 nm. The mechanism of the formation of hierarchical patterns was suggested. Ordering of the pores was quantified with the Voronoi tessellations and calculation of the Voronoi entropy. The Voronoi entropy for the large scale pattern was S v o r = 0.6 − 0.9 , evidencing the ordering of pores. Measurement of the apparent contact angles evidenced the Cassie-Baxter wetting regime of the porous films.