X-ray fluorescence method was proposed for a determination of major elements in samples of snow cover solid phase collected in the urban areas of the Irkutsk region near aluminum smelter and combined heat and power plant. The limitation of the analyzed sample mass, which in some cases does not exceed 50 mg, as well as the features of the elemental composition (high Al and low Si contents) require a special methodological approach to quantitative elemental analysis. Due to the lack of matrix-matched certified reference materials, the calibration set includes certified reference materials of igneous and sedimentary rocks as well as aluminum ore samples. Results of X-ray fluorescence method were compared with the results obtained by reference methods including atomic absorption, atomic emission and spectrophotometry methods. It showed that it is necessary to use samples of snow cover solid phase analyzed by reference methods as a calibration set for X-ray fluorescence analysis, which ensures the quantitative determination of major elements (Na, Mg, Al, Si, P, K, Ca, Ti, Mn and Fe). These elements are important for environmental pollution investigation. Al was discovered as a main pollutant produced by aluminum smelter, Si, Ca, Ti, Mn, and Fe - by combined heat and power plant.