The frequent co-existence of arsenic (As) and lead (Pb) necessitates the investigation of clean-up technologies for multi-metal(loid)s. Field survey and hydroponic experiments were conducted to elucidate the co-accumulation of As and Pb in Pteris vittata L. The P. vittata population isolated from a Pb-Zn mine in Yunnan province, China is a potential extractor of As and Pb co-contamination. Hydroponic experiment found that the highest frond As and Pb concentrations in mining population of P. vittata reached 12.2 and 0.99 g kg(-1), respectively. The interaction between As and Pb in P. vittata was further more disclosed. Pb (2 mg L-1) improved the frond As concentration by 60 to 150 % in mining populations of P. vittata. Micro-X-ray absorption spectroscopy indicated that under the combined exposure of As and Pb, the As content in the rhizoid epidermis increased by about 10-fold, and the As(V) percentage increased in each rhizoid tissue, as compared with that under As exposure alone. The co-absorption of As and Pb on the epidermis and the enhanced transportation of As(V) from epidermis into the rhizoid were suggested to contribute to the increased As accumulation.