Plant species, spatial variability in plant diversity and vegetation cover were recorded at a French timber treatment site with Cu-contaminated soils (65–2600 mg/kg). Shoot biomass, shoot Cu concentration and accumulation were determined for each plant species found on 168 quadrats with increasing total Cu in soil and soil solution. A total of 91 species occurred on the site including four considered as invasive (Cyperus eragrostis, Phytolacca americana, Senecio inaequidens, and Sporobolus indicus). Species richness, Shannon index, vegetation cover and plant biomass decreased as soil Cu increased. At low soil Cu, members of the Poaceae were most frequent followed by Fabaceae, Rosaceae, and Asteraceae. At high soil Cu, Poaceae were again most frequent. Species known to form Cu-tolerant populations, i.e. Agrostis capillaris, A. stolonifera and Rumex acetosella were present. Shoot Cu concentration and accumulation were higher in plants growing in the most contaminated soils. At 2142 mg Cu/kg soil, shoot Cu accumulation peaked at 6 mg Cu/m² in A. capillaris, and its shoot Cu concentration (364 mg Cu/kg dry weight) exceeded the fodder Cu threshold for domestic livestock. In less Cu-contaminated soils some candidates were identified for sustainable phytoremediation with a potential financial return.