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Self‐standing and coated‐on‐glass films were prepared from polymer–inorganic ormosils, using the cationic polymer poly(methacrylamide propyl quaternarydimethyldodecyl bromide). The inorganic compound was grown in sol–gel reactions based on methyltriethoxysilane (MeTES), with or without addition of the titanium‐precursor: tetraisopropyl orthotitanate. As evidenced by thermogravimetric analysis and differential scanning calorimetry data, the thermal properties of the films are highly dependent on the internal morphology. Inorganic granules with a TiO2 rich shell have a more polar surface, which stimulates stronger electrostatic interactions with the polymer, hence, a reduced mobility for the amino end and a smaller probability to have amino ends engaged in interactions at the surface of the granules. Coated‐on‐glass films drawn from pure cationic polymer suffer from partial dewetting. Topographic and force‐versus‐distance recordings using atomic force microscopy showed a change in the energy balance and no dewetting regions were encountered for polymer/MeTES based composites. However, because of nongrafted polymer, these films are not immune at washing with water/ acetone. Explorations of antibacterial activity against the gram‐negative bacteria, Pseudomonas aeruginosa, were done using ormosil films with alkoxysilanes combinations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [ABSTRACT FROM AUTHOR]