The amount of glomalin-related soil protein (GRSP), a glycoprotein produced by arbuscular mycorrhizal fungi (AMF), its contribution to the sequestering of Cu and Zn in the soil, and the microsite variation of other soil traits (pH, water-stable aggregates--[WSA], soil organic carbon--[SOC]) was studied in a semi-arid Mediterranean ecosystem near a copper smelter and affected by deposit of metal-rich particles since 1964. Rhizospheric (R) and non-rhizospheric (NR) soil of four representative plants (Argemone subfusiformis, Baccharis linearis, Oenothera affinis and Polypogon viridis) was analyzed. The results showed a strong variability in GRSP (6.6-36.8 mg g(-1)), Cu content (62-831 mg kg(-1) for the total Cu and 5.8-326 mg kg(-1) for the available Cu) and pH (4.2-5.5) in the different plant and rhizospheric zones analyzed. A strong relationship between the GRSP with the soil Cu and Zn contents was found (r=0.89 and 0.76 for Cu and Zn respectively, p<0.001). The GRSP-bound Cu ranged from 3.76 to 89.0 mg g(-1) soil and represents 1.44-27.5% of the total Cu content in soil. Moreover, the WSA reached 89% in P. viridis R. For this plant, the C contained in GRSP represented up to 89% of SOC, and this coincided with the most extreme conditions of soil degradation within the ecosystem (the highest content of heavy metals and low pH values). This study provides evidence on the role of the GRSP in Cu and Zn sequestration and suggests a highly efficient mechanism of AMF to mitigate stress leading to stabilization of soils highly polluted by mining activities.