Plants hare the ability to accumulate the long-lived fission product PTC. In this work, an attempt was made to separate and characterize technetium species induced by spinach plants (Spinacia oleracea L.) grown on a TcO4- containing nutrient solution. Combination of data obtained with selective extraction (ammonium sulfate, acetone, di-ethyl ether, and 8-hydroxyquinoline in chloroform) and chromatography (size-exclusion chromatography and reversed-phase ion-pair chromatography) gave us insight into Te speciation in spinach plants. The following classes of Tc species in spinach leaf homogenate were found after an incubation period of 11 d: TcO4- (ca. 7%), Tc-V-cysteine (ca. 25%), Te bound to insoluble cell-wall polysaccharides (ca. 17%), Te bound to proteins (ca. 26%), and hydrophilic non protein Tc species (ca. 25%). These results may yield a new insight into the metabolic pathways of Te in plants.