We show how the combined use of the methods of Rutherford backscattering of ions and X-ray fluorescence analysis under conditions of total external reflection of the flow of exciting hard X-ray radiation and registration of the X-ray radiation output during ion excitation allows to effectively diagnose the elemental composition of thin-film coatings and films of dry residues of liquids. These methods and the features of their experimental application are briefly described. Examples of the complex methodological analysis of real objects are given. The possibility of increasing the efficiency of the methods of X-ray fluorescence analysis of materials due to the inclusion in the X-ray optical schemes of experimental measurements of flat X-ray waveguide resonators is indicated.