The grazing incidence X-ray diffraction from the 2D polar crystallites of organic dye molecules on an aqueous subphase was measured. The structure of the 2D crystallites shows a dependence on the subphase composition, and this dependence corresponds well to the results obtained from Langmuir-Blodgett films, which consist of the multilayer of the 2D crystallites deposited on the solid planar supports. © 2003 Taylor & Francis.