Honeycomb-patterned polyalkylcyanoacrylate (PACA) films were prepared from the chloroform solutions of alkylcyanoacrylate (ACA) by breath figures (BFs) method. Condensed water droplets on the solution surface acted not only as templates to endow the ordered structure but also as initiators to trigger the polymerization of ACA. After the polymerization started, the in situ formed polymer chains self-assembled around the water droplets, structuring PACA film with a hexagonal arrangement of holes. This was the first time that polymerization was introduced to breath figures method. The formation mechanism and the influencing factors, including substrates, relative humidity, and solution concentrations were investigated. Hela cells were cultured on both flat and honeycomb-like PACA films to investigate their application as biomaterials. (C) 2010 Elsevier Inc. All rights reserved.