A method for determining ∼0.01 μg/g or more of tellurium in ores, concentrates, rocks, soils and sediments is described. After sample decomposition and evaporation of the solution to incipient dryness, tellurium is separated from > 300 μg of copper by co-precipitation with hydrous ferric oxide from an ammoniacal medium and the precipitate is dissolved in 10 M hydrochloric acid. Alternatively, for samples containing ⩽ 300 μg of copper, the salts are dissolved in 10 M hydrochloric acid. Tellurium in the resultant solutions is reduced to the quadrivalent state by heating and separated from iron, lead and various other elements by a single cyclohexane extraction of its xanthate complex from ∼9.5 M hydrochloric acid in the presence of thiosemicarbazide as a complexing agent for copper. After washing with 10 M hydrochloric acid followed by water to remove residual iron, chloride and soluble salts, tellurium is stripped from the extract with 16 M nitric acid and finally determined, in a 2% v/v nitric acid medium, by graphite-furnace atomic-absorption spectrometry at 214.3 nm in the presence of nickel as matrix modifier. Small amounts of gold and palladium, which are partly co-extracted as xanthates if the iron-collection step is omitted, do not interfere. Co-extraction of arsenic is avoided by volatilizing it as the bromide during the decomposition step. The method is directly applicable, without the co-precipitation step, to most rocks, soils and sediments.