Separation and preconcentration via of liquid ion exchange which is one of solvent extraction application was very important as separation method. This book involves the applicability of liquid ion exchange by using of super molecules such as crown ethers such as 12C4, 15C5,18C6, DB18C6, DCH18C6, DB24C8 and cryptands C221, C222 in presence of alkali and alkaline earth metal cation to form liquid ion exchanger used to extract chloroanion complexes of Pb (II) and Al (III). Chloroform used as an organic solvent to dissolve crown ethers and cryptands. Pb (II) extracted from HCl media, whereas Al (III) from neutral media. As well prepared calibration curves for spectrophotometric determination of metal ions under study in environmental and vital samples, the different samples were prepared according to wet digestion method.