In terms of investigating the authentic plant biomonitoring and phytoextraction potentials, the samples of soils and shoots of the sun spurge (SS) and common nettle (CN), were collected near several polluted water bodies in the close vicinity of the copper mining/metallurgical complex in Bor (Serbia) and characterized with regard to the content of heavy metal(oid)s: As, Cd, Pb, Cu, and Zn. The methods applied in this work such as inductively coupled plasma-mass spectrometry, one-way analysis of variance, Pearson's correlation study, hierarchical cluster analysis, and the calculation of bioaccumulation rates (expressed through the so called mobility ratios, MRs), provided very informative data on the potentials of both investigated pioneer species. The most important findings were: 1) In most cases, SS was more effective in metal extraction/translocation/bioaccumulation than CN, and especially with regard to Cu; in this particular case, extremely high concentrations were recorded and also, some significant MRs were calculated, which may be a signal of its promising potential for Cu-phytoremediation, practically, Cu-phytoextraction; however, generally, the values of most calculated MRs were very low (<1, for both plants); 2) The shoots of both plants reflected soundly the current status of metal presence in the studied environment and they can be recommended for seasonal screenings of a general level of metal pollution in the areas of interest; however, specifically, they cannot reflect quite correctly the level of soil pollution; 3) Soil Cu, and As were detected in alarming concentrations. • Heavy metals were evaluated in Euphorbia helioscopia L. and Urtica dioica L. • Chemometry provided useful data on plant biomonitoring and phytoextraction potentials. • The most significant bioaccumulation rates were calculated for Cu in sun spurge. • Both plants can be very useful in biomonitoring and sun spurge in Cu-phytoextraction. [ABSTRACT FROM AUTHOR]