Organosilanes are often used in commercial sizings for glass fibres to provide wettability with the resin and promote strong interfacial adhesion to the matrix in a fibre reinforced polymer composite. The silane treatment is introduced as part of a complex deposition from an aqueous emulsion immediately at the spinaret and determines the optimum properties of the cured composite. To understand the interaction of organosilanes contained in sizings for glass surfaces, XPS was used to investigate the adsorption of -aminopropyltriethoxysilane (APS) from a simple sizing system containing a polyurethane (PU) film former. It has been found that both APS and the sizing (containing APS and PU) deposits on E-glass fibre surfaces contained components of differing hydrolytic stability. The differences observed in the AFM images of APS coated E-glass fibres before and after water extraction also confirmed that the APS deposit contained components with different water solubility.