This article presents results on the liquid-liquid extraction studies for the separation of tannic acid from aqueous and hydro-alcoholic medium. These liquid-liquid extraction studies aim to investigate the suitable hydrophobic solvent or solvents combination and to optimize the extraction conditions for the quantitative separation of tannic acid from aqueous and hydro-alcoholic feed. A mixture of hexanol and octanol is found to be most suitable for the quantitative extraction of tannic acid from aqueous feed solution. One hour equilibration time was enough to reach equilibrium. With increase in tannic acid concentration from 10mg center dot L-1 to 900mg center dot L-1 in the feed solution, the extraction of tannic acid was found to be decreasing. The concentration of ethanol plays an important role in controlling the solubility of feed in hydrophobic solvent. The suitable solvent combination was tested for the selectivity for individual polyphenol from a mixture of tannic acid and Epi-catechin and it was found that a combination of hexanol and octanol was good for tannic acid extraction whereas decanol was more selective for Epi-catechin extraction.