The toxicity, mobility and bioavailability of Cr, a versatile industrial metal and a contaminant, depends on its chemical form, viz: Cr(lll) and Cr(VI). It may enter humans through plants grown on contaminated soil or irrigated by contaminated water. The phytoavailability and transfer through agricultural food chains requires an understanding of mechanisms of Cr uptake and translocation by plants. Xylem sap transports both nutrient and non-nutrient ions after absorption by roots to aerial parts of the plant. lt transports cations by complexation with organic ligands. Trivalent chromium, though prone to hydrolysis, also complexes O donor ligands. The chemical form in which Cr(lll) is transported by xylem sap was investigated. ln vitro studies were performed by mixing the xylem sap of maize plants at three stages of plant growth with radiotagged Cr(III). The speciation change was investigated after 10 days and 30 days by anion and cation exchange elution chromatography. The elution curves were compared with those of pure Cr(III) and Cr(III) complexes of different synthetic acids. Complexation of Cr(III) with ligands of xylem sap especially with carboxylates was evident. Cationic Cr(III) was vitally being transported as anionic organic complex species. The major species seemed to be that of Cr(III)-citrate. Citric acid was the major complexing acid of xylem sap as determined by HPLC. These mobile and soluble complexes may get immobilized and stored in leaves and other edible plant parts. This may also be a mechanism used by plants for detoxification of toxic Cr(VI) which may become reduced and then complexed.