Arsenic-contaminated soil is one of the major arsenic sources for drinking water. Phytoremediation, an emerging, plant-based technology for the removal of toxic contaminants from soil and water, has been receiving renewed attention. Although a number of plants have been identified as hyperaccumulators for the phytoextraction of a variety of metals, and some have been used in field applications, no hyperaccumulator for arsenic had been previously reported until the recent discovery of Brake fern (Pteris vittata), which can hyperaccumulate arsenic from soils. This finding may open a door for phytoremediation of arsenic-contaminated soils. Speciation and distribution of arsenic in the plant can provide important information helpful to understanding the mechanisms for arsenic accumulation, translocation, and transformation. In this study, plant samples after 20 weeks of growth in an arsenic-contaminated soil were used for arsenic speciation and distribution study. A mixture of methanol/water (1:1) was used to extract arsenic compounds from the plant tissue. Recoveries of 85 to 100% were obtained for most parts of the plant (rhizomes, fiddle heads, young fronds and old fronds) except for roots, for which extraction efficiency was approximately 60%. The results of this study demonstrate the ability of Brake fern as an arsenic hyperaccumulator. It transfers arsenic rapidly from soil to aboveground biomass with only minimal arsenic concentration in the roots. The arsenic is found to be predominantly as inorganic species; and it was hypothesized that the plant uptakes arsenic as arsenate [As(V)I and arsenate was converted to arsenite [As(III)] within the plant. The mechanisms of arsenic uptake, translocation, and transformation by this plant are not known and are the objectives of our on-going research.