Recently discovered As-hyperaccumulator ferns hold promise for phytoremediation of As-polluted soils. We investigated changes in the rhizosphere characteristics of Pteris vittata (Chinese Brake fern) relevant for its use in phytoextraction. Plants were grown in rhizoboxes filled with soil containing 2270 mg kg-1 As. Dissolved organic carbon (DOC) concentrations in rhizosphere soil solution were increased by 86% and appeared to enhance total Fe solubility due to complexation reactions. Despite substantial removal of As by the fern, As was not significantly decreased in the rhizsophere soil solution after one cropping, apparently due to the large buffer capacity of the soil and possibly because of ion competition with DOC. However, the difference between 0.05 M (NH4)2SO4-extractable labile As in bulk and rhizosphere soil accounted for 8.9% of total As accumulated in the fern, indicating that As was mainly acquired from less available pools. Moreover, As depletion in the rhizosphere and limited resupply from less available pools were indicated by a 19.3% decreased As flux, measured using the technique of diffusive gradients in thin films (DGT). Modeling of the DGT−soil system was able to show that the rate of release from solid phase to solution in the rhizosphere was one-third of that in the bulk soil. Applying the remedial strategy of bioavailable contaminant stripping, which aims at diminishing the phytoavailable pollutant fraction, DGT can be used as a monitoring tool to evaluate the efficiency of phytoextraction and to study the potential resupply of bioavailable pools after phytoextraction has ceased.