A novel method has been developed for the solvent extraction of Potassium (I) from 0.001M picric acid with 0.001M Dicyclohexano-18Crown-6in nitrobenzene. Potassium (I) from the organic phase was determined flame emission spectroscopy at 767 nm. Extraction was found to be quantitative in the range of 7-10 Mpicric acid. When the concentration of Dicyclohexano-18Crown-6 was varied from 0.05-20% in nitrobenzene, it showed that optimum concentration was 3%. Amongst diluents like nitrobenzene was found to be an effective diluent. Effect of shaking time, concentration of metal ion. Tolerance limits of various diverse ions were studied. Potassium (I) was separated from associated elements in its ternary mixtures with Sb(III), Bi(III) and Cu(II), Au(III). The proposed method was applied for separation and determination of Potassium (I) in rocks and foodstuffs.