A successful methodology for obtaining hybrid films which allow thermal triggering and continuous, irreversible, control of their hydrophilicity/hydrophobicity nature was developed. Two types of poly (dimethylsiloxane)-silica (PDMS@SiO2) films were prepared for that purpose: A hydrophilic film in which the thermal treatment causes an irreversible gradual increase of hydrophobicity; and a hydrophobic film that turns more hydrophilic upon thermal treatment. The opposite directionality of the change is dictated by the film substrate, on which the same hybrid is deposited. In both cases the thermal treatment induced a phase separation which caused the change in hydrophobicity. The magnitude of change in hydrophilicity/hydrophobicity is continuously controllable in both types of films by either the temperature or heating time. The films were characterized before and after heating by a variety of methods, including contact angle (CA) measurements with the sessile drop and the tilting plate methods, and by X-ray photoelectron spectroscopy (XPS) analysis. A thorough kinetic study was carried out, following the progress of the changes in the wettability property of the surfaces. The kinetics analyses proved that the changes in the wettability in all cases are due to phase separation processes, the directionality of which is determined by the treatment of the substrate on which the films are deposited. By monitoring the change of wettability (ACA) at various temperatures, an Arrhenius plot was obtained from which the activation energy and Arrhenius pre-exponential factor for the phase separation were derived, corroborating the proposed mechanism. To the best of our knowledge, this is the first use of phase separation behavior of a hybrid film in order to apply irreversible, thermally controllable change of surface wettability, tailored to proceed in opposite directions, and the first kinetic study of such a process. (C) 2017 Elsevier Inc. All rights reserved.