Here we present results of a survey conducted to identify and characterize spontaneously growing arsenic-tolerant plant species of the area around the old arsenic/gold mine in ZlotyStok (Poland), with respect of their potential use in phytoremediation. Plants and soil from their rhizosphere were sampled and analyzed for concentrations of As and accompanying Mn, Fe, Mg, Ca, Al, Cu, Zn, Ba, Pb, Ni, Cs, V, Cr, Sr, Rb, Bi, Mo and U. The soil contained primarily very high As, Pb and Al concentrations (up to 7,451, 1,058 and 31,272 mg/kg respectively). The ability of identified species to modify the amount of bioavailable arsenic in their rhizosphere was determined by single extractions of soil samples with the use of water, phosphate buffer, EDTA, and acetic acid. Although As-hyperaccumulators were not found, Calamagrostis arundinaca was identified as a new species which successfully carried out the natural phytoextraction of arsenic. This plant was able to increase substantially the arsenic availability in the soil, and likely due to efficient uptake decreased the total As concentration within the root zone by around 40% relative to the reference soil. Thus, it has high potential for phytoremediation. The lowest amount of available arsenic was found in the rhizosphere of Stachys sylvatica, the species with the lowest As shoot concentration (compared with other plant species). It was proposed as a good candidate for phytostabilization.