Elemental composition of Vaccinium myrtillus L. and Vaccinium vitis-idaea L. has not been determined yet in detail. In our study, a scanning electron microscope coupled with an energy dispersive X-ray analyser (SEM–EDX) ensured the determination of 15 elements in the leaves of Vaccinium sp. growing in the control and the mine polluted locality. The soil elemental analyses showed a higher content of 11 elements from all determined in the mine-influenced samples. Elemental analyses of the control leaves showed the highest contents of all determined elements for V. vitis-idaea, except for carbon. The impact of pollution on V. myrtillus leaves caused significant increase in oxygen, natrium, magnesium, sulphur, chlorine, potassium and calcium content. The contents of carbon, nitrogen and silicon decreased substantially. In the case of the V. vitis-idaea leaves, the content of most of elements reduced, and in the case of six elements, even significantly. A significant increase was recorded for carbon, iron and copper. The effect of the environment has influenced the production of phytochemicals, assessed by HPLC–DAD. The production of flavonoids (hyperoside, isoquercetin) increased significantly in V. myrtillus and decreased to a detectable minimum in V. vitis-idaea. In the case of chlorogenic acid, arbutin and hydroquinone, their levels changed minimally in V. myrtillus, but significantly more in the V. vitis-idaea leaves. The importance of elemental analyses lies in detecting the presence of toxic elements or their harmful concentrations in plants that are the source of food or dietary supplements.