The fact that heavy metals can enter various domains of the plant system through foliar pathways spurred us to explore if the fronds of the Chinese brake fern (Pteris vittata L.), a hyperaccumulator of arsenic, a carcinogenic metalloid, was proficient in absorbing arsenic in the form of sprays. The specific objective of this study was to investigate the impact of frond age, form of arsenic, and time of application on the absorption of foliar-applied arsenic by the brake fern; also examined were the effects of foliar sprays on surface ultrastructure and arsenic speciation in the frond following absorption. Foliar sprays of different arsenic concentrations (0, 50, 100, 200, and 400 ppm) were applied to young and fertile fronds. A positive linear relationship existed between arsenic concentration and absorption; the arsenic concentration of fronds increased from 50 to 200 ppm. Time-course analysis with excised pinnae indicated an initial linear increase followed by a plateau at 48 h. The young fronds with immature sori absorbed more arsenic (3100 ppm) than the fertile mature fronds (890 ppm). In the frond, the arsenic absorption was greatest in the lamina of the pinnae followed by the sori and the rachis. Applying arsenic during night (20:00-22:00 h) or afternoon (12:00-14:00 h) resulted in greater absorption of arsenic than the application in the morning (08:00-10:00 h). The arsenic absorption was greater through abaxial surfaces than through adaxial surfaces. The brake fern absorbed more arsenic when it was applied in the form of arsenite. Regardless of the form of arsenic and the surface it was applied to, arsenic occurred as arsenite, the reduced and the most toxic form of arsenic, after having been absorbed by the fronds. Scanning electron microscopy revealed no surface morphological alterations following all arsenic sprays. The study unequivocally illustrated that the Chinese brake fern absorbed foliar-applied arsenic with great efficiency. Consequently, the arsenic concentrations in the fronds transcended the levels of hyperaccumulation; such a characteristic could be exploited in the phytoremediation of groundwater contaminated with arsenic.