The molecular orientation at the surface of polyimide (PI) alignment layers used for liquid crystal displays has been determined using X-ray absorption spectroscopy (NEXAFS). The second moments of the orientation distribution function obtained from a detailed analysis reveal that, upon rubbing, the PI substrates develop biaxiality and an inclination of a few degrees. For a nematic liquid crystal (LC) in contact with these alignment layers, the pretilt angle was determined and revealed a weak correlation with buffing strength.