Multilayer structures composed of poly(allylamine hydrochloride) (PAH) and Nafion were fabricated on glass substrates by layer-by-layer assembly. Some of the multilayers demonstrated spontaneous changes in contact angle of water and oil due to flip-flop movements of free sulfo groups in the Nafion layer, and the multilayers eventually possessed water repellency in air and oil repellency in water. The repellencies were enhanced by applying primer layers that were formed using SiO2 fine particles to increase surface roughness. Compared to typical hydrophobic and oleophobic surfaces, the multilayers showed practical levels for a use as soil release coatings. (C) 2014 Elsevier B.V. All rights reserved.