Liquid films of different silicate esters were deposited front volatile solvents on hydroxylated and hydrogen-passivated silicon surfaces. We show that adsorption of silicate ester molecules and the resulting structural morphology of the liquid films not only are determined by attractive van der Waals forces with contributions front electrostatic interactions between the silicone ester moieties and oxide surface sites but also can be tuned by modifying the substrate surface or by changing the liquid solvent interactions. Our results also show the importance of the conformational properties of liquid molecules and their rearrangements at the liquid/solid interface for controlled solvent-assisted film deposition.