ABSTRACTThis work aims to investigate the influence of the substrate temperature on low‐pressure plasma polymerization processes. Emphasis is placed on the mechanical properties and growth mechanism of the plasma polymer films (PPFs). For this purpose, two precursors are considered, differing only by their unsaturation degree: 2‐propen‐1‐ol (CH2═CH–CH2–OH) and propan‐1‐ol (CH3–CH2–CH2–OH). Although propan‐1‐ol‐based PPFs behave like hard elastic solids, 2‐propen‐1‐ol‐based coatings evolve from a liquid film to an elastic solid on increasing the substrate temperature. This behavior is understood considering the evolution of the glass transition temperature of PPFs. The latter is correlated with the cross‐linking degree of the polymeric network governed by the energy density of bombarding ions on the growing film.