Self-assembled films made of ladder [2-(carboxymethylthio)ethyl]-polysilsesquioxanes adsorbed on mica are stable within a wide temperature range (293-373 K). A thermally induced transformation, resulting in a significant decrease of free surface energy but not in a collapse of macromolecules in the adsorbed film was observed only at 393 K. The unique behaviour has been ascribed to a specific rearrangement of hydrogen bonds between COOH groups. It is irreversible under ambient conditions, but the structural features and properties of the self-assembled film can be reverted to the primary state if the sample is kept in humid atmosphere (steam). Wetting angle measurements as well as microscopic (AFM) and spectroscopic (ATR FTIR, ARXPS) studies were carried out to evaluate changes in the surface morphology and its physiochemical properties. The studied [2-(carboxymethylthio) ethyl]-polysilsesquioxanes were also used as a printing ink on native mica. The micropatterns exhibited all the characteristic properties of the self-assembled films, which can be exploited for the formation of precisely localized surface textures of specific chemical composition and specific free surface energy. (C) 2016 Elsevier Ltd. All rights reserved.