The favourable nutritional profile of mushrooms, high proportion of indigestible fibres, and antioxidative and flavour constituents have attracted increasing interest of researchers and consumers. However, the ability of some species to accumulate and even hyperaccumulate various toxic elements is distinct from that of other foods. Moreover, some mushrooms have been highly contaminated by radioactive fallout from the Chernobyl disaster in 1986; therefore, 137Cs and, to a lesser extent, 134Cs were detected in the following years in some edible species. Spectrometric methods, e.g., ICP–MS and ICP–AES, have been reported to be useful for quantifying the multielemental profile of fruiting bodies (caps and stalks) of mushrooms. Original data have been processed mostly with PCA, CA and HCA and significantly less often with CDA, PLS–DA, SVM, SD, MSC and other methods. It has been possible to assess important parameters, e.g., interregional and interspecies variations, as well as the bioaccumulation abilities of mushrooms, in relation to the elemental composition of the soil substratum; additionally, it has been possible to assess the impact of pollution on the elemental composition of mushrooms and other parameters.