Synchrotron radiation X-ray absorption near edge structure was employed to study the arsenic (As) speciation in 13 Pteris vittata L. populations collected from 7 provinces, cities, and autonomous regions in China. As in roots of P. vittata was mainly combined with oxygen (0), with a small amount of As combined with glutathione (GSH). Populations from Hunan and Guangxi provinces showed higher percentages of As-GSH in soots. As in roots of P. vittata was predominated with As( V), with the percentage of As(V) V) to the total As being 59. 6 +/- 0. 6%similar to 83. 8 +/- 3. 8%. The As(V) V) percentage was in the order of HN5<GX2<HN1<CQ<GX1<GD<HN3<HN4<GX3<HN2<TW<AH<FJ. Similar with that in roots, As in shoots was also mainly combined with 0, with few combined with GSH. The percentage of As-GSH to the total As was in the order of GD>HN3>HN1>TW>CQ>AH>FJ>HN5>HN2>GX2>GX3>HN4>GX1, within the range of 2. 4%similar to 12. 9%. Different from that in roots, As in shoots was predominated with As(III), with no As() detected. The disclosure of As speciation in the roots and shoots of P. vittata contributes to the future research on As accumulation mechanism.