Arsenic (As) contaminated soils and waters are becoming major global environmental and human health risks. The identification of natural hyperaccumulators of As opens the door for phytoremediation of the arsenic contaminant. Pteris vittata is the first identified naturally evolving As hyperaccumulator. More than a decade after its discovery, we have made great progress in understanding the uptake, transport, and detoxification of As in the fern. The molecular mechanisms controlling As accumulation in P. vittata are now beginning to be recognized. In this review, we will try to summarize what we have learned about this As accumulator, with particular emphasis on the current knowledge of the physiological and molecular mechanisms of arsenic phytoremediation. We also discuss the potential strategies to further enhance phytoextraction abilities of P. vittata.