Liquid-liquid chromatography was used to separate amino acids, which was considered a breakthrough in biochemistry. Here, in case of liquid-liquid chromatography, liquid is stationary phase that is mutually insoluble with mobile phase. The stationary liquid phase is absorbed on the surface of substrate, forming a thin layer and mobile phase could then flow over the stationary phase without removing it from the column. Derivation of distribution coefficient has been given in this chapter in a very lucid manner. Application of liquid-liquid chromatography includes detergent removal, separation of steroids, bile acids, mycotoxins, pesticides, phenols and trace metals, etc.; however, special emphasis has been given to pesticide residues analysis. Different techniques of solvent microextraction in backdrop of pesticide residues have been highlighted in this chapter with graphical representation and in a tabular format.