The review concerns modern experimental methods of structure determination of thin films of different nature. The methods are based on total reflection of X-rays from the surface and include X-ray reflectivity, grazing-incidence X-ray scattering and X-ray standing waves. Their potential is exemplified by the investigations of various organic macromolecular systems that exhibit the properties of semiconductors and are thought to be promising as thin-film transistors, light-emitting diodes and photovoltaic cells. It is shown that combination of the title methods enable high-precision investigations of the structure of thin-film materials and structure formation in them, i.e., it is possible to obtain information necessary for improvement of the operating efficiency of elements of organic electronic devices. The bibliography includes 92 references.