Copper (Cu) concentration in agricultural soils often exceeds toxicological limits due to application of Cu-based fungicides. The potential of weeds for their use as functional cover plants in vineyard management and phytoremediation practices is little explored. We identified five weed species widely present in vineyards and assessed their Cu accumulation from eleven Mediterranean vineyards (soil Cu: 60-327 mu g g(-1)) and two adjacent control sites (soil Cu: 15-30 mu g g(-1)). Soils and plants were characterized by their physico-chemical properties and nutrient content. We applied multivariate techniques to analyze relationships between soil properties and leaf nutrient composition. Copper tolerance and accumulation traits were further tested in hydroponics using a series of CuSO4 concentrations (0.1-16 mu M). Under field conditions, the highest Cu concentration in both roots and leaves were found in Lolium perenne (221 and 461 mu g g(-1), respectively), followed by Plantago lanceolata, Rumex obtusifolius and Taraxacum officinale (>100 mu g g(-1) Cu in leaves). Only one species, Trifolium repens, did not accumulate remarkable Cu concentrations. Overall, and as revealed by the multivariate analyses, leaf Cu concentration was driven by soil Cu content, soil texture, organic matter, nitrogen, and Cu uptake into roots. However, functional regression analysis and controlled experiments suggested that Cu might be additionally absorbed from the deposits on the leaf surface related to the Cu-fungicide treatments and soil dust. Our study highlights the importance of intra-specific variability in Cu accumulation among weed species in Cu-contaminated agricultural soils. Further validation of these findings under controlled conditions could provide essential insights for optimizing management and remediation strategies.