This work aims to provide new insights into the link between the growth mechanisms of functionalized plasma polymer films (PPFs) and the substrate temperature (TS). By means of AFM‐based techniques, it has been demonstrated that the mechanical behavior of the coatings is dramatically affected by TS and the precursor employed (i.e., 1‐propanethiol or 1‐propylamine). While propylamine‐based PPFs behave as hard elastic materials regardless of TS, propanethiol‐based PPFs evolve from viscous liquids to elastic solids with increasing TS. This behavior can be understood considering the glass transition temperature of PPF. For both precursors, the latter is correlated to the cross‐linking density controlled through the energy density brought by positive ions to the growing film. [ABSTRACT FROM AUTHOR]