A method for determining 0.0005% or more of total aluminium in high- and low-alloy steels, iron and ferrovanadium is described. Iron, chromium and other matrix elements are separated from aluminium by electrolysis with a mercury cathode and aluminium is separated from tungsten, titanium, vanadium and phosphate by chloroform extraction of its acetylacetone complex at pH 6.5 from an ammonium acetate-hydrogen peroxide medium. The extract is evaporated to dryness and organic material is destroyed with nitric and perchloric acids. Aluminium is determined by atomic-absorption spectrophotometry in a nitrous oxide-acetylene flame, at 309.3 nm, in a 5% v/v perchloric acid medium containing 1000 mug of sodium per ml. Acid-soluble and acid-insoluble aluminium can also be determined. The method is also applicable to copper- and nickel-base alloys. Results obtained by this method are compared with those obtained spectrophotometrically with Pyrocatechol Violet, after the separations described above followed by the separation of the residual co-extracted iron and copper by a combined ammonium pyrrolidinedithiocarbamate-cupferron-chloroform extraction from 10% v/v hydrochloric acid medium.