Quantum chemical calculations have been carried out on the grafting of chain organosilane compounds on SiO2-hydroxylated solid surfaces. It is shown that a single molecule interacting with the surface lies flat to it, inhibiting further homogeneous film growth. This adsorption exhibits two molecule/surface interactions: a covalent bond on one side of the molecule and a hydrogen bond on the other side. We then investigate the possible preorganization of the molecules before grafting due to the presence of water molecules either in the gas/liquid phase or near the surface. This gives rise to the formation of dimerized chains. We then demonstrate that this preorganization process prevents subsequent lying flat of the molecules to the substrate after grafting. Energetics and associated configurations of the overall deposition process are discussed in detail and provide new insights on the understanding of the formation of self-assembled homogeneous organic films on microelectronics-type substrates.