The adsorption of several prehydrolyzed alkoxysilanes onto the surface of cellulosic fibers in ethanol/water mixtures has been studied quantitatively. The corresponding isotherms show the formation of a monolayer followed by further adsorption. The nature of the fourth substituent on the silane plays a specific role on the features of this association. Whereas at room temperature only dispersive and polar attractive interactions occur, heating above 100 °C produces condensation reactions resulting in covalent bonding between the substrate and the silane forming the monolayer. As a result of this investigation, the possibility of calling upon this surface modification in order to compatibilize cellulosic fibers with polyolefinic matrixes for the elaboration of composite materials seems to be a promising strategy.