The formation and growth of self-assembled octadecylsiloxane monolayers on native silicon and mica substrates have been studied using atomic force microscopy, ellipsometry, and infrared spectroscopy. Submonolayer ODS films of varying surface coverages were prepared by immersing the substrates into dilute solutions of octadecyltrichlorosilane in toluene for different periods of time, and the submonolayer film structures were compared between mica and silicon substrates for different water contents of the adsorbate solutions and for different time delays between solution preparation and substrate immersion (solution age). It was found that, in general, both a continuous growth (formation of disordered, liquidlike submonolayers) and an island-type growth (formation of organized assemblies with vertically aligned hydrocarbon chains) are involved in the formation of ODS monolayers, whereby the relative contributions depend strongly on the solution properties. With increasing water content or increasing age of the adsorbate solution, island-type growth is strongly favored on both silicon and mica surfaces, which indicates the kinetically controlled formation of larger, preordered aggregates of silanol molecules as the primary hydrolysis products in solution. For identical conditions of film preparation, both the degree of structural order in the submonolayer films and the overall adsorption rate was found to be higher on mica in comparison to silicon. The higher structural order was interpreted as a consequence of the lower hydroxyl group concentration and a correspondingly enhanced surface diffusion rate of weakly bound film molecules on a mica substrate. The enhanced adsorption rate, on the other hand, points to some additional activation of a mica surface with respect to silanol adsorption, which might be related to its ionic composition containing mobile surface charges in contrast to the covalent, neutral character of a native silicon surface.