N-n-Octylaniline in xylene is used for the extractive separation of palladium(II) from hydrochloric acid medium. Palladium(II) was extracted quantitatively with 10 ml of 2% reagent in xylene from 0.5-2 M hydrochloric acid medium. It was stripped from the organic phase with 1:1 ammonia and estimated spectrophotometrically with pyrimidine-2-thiol at 420 nm. The effects of metal ion, acids, reagent concentration and of various foreign ions have been investigated. The method affords binary separation of palladium(II) from iron(III), cobalt(II), nickel(II) and copper(II) and is applicable to the analysis of synthetic mixtures and alloys. The method is fast, accurate and precise.