Grazing incidence x-ray diffraction is used to characterize the molecular arrangement of ultrathin Langmuir-Blodgett (LB) multilayers. Using two angles of incidence of the beam allowing its penetration either throughout the complete depth of the film or only through the external layers, we show that it is possible to discriminate between the molecular packing of the deeper monolayers and that of the external monolayers of the LB film.