Hydrotropes, such as sodium alkyl benzene sulfonates and sodium butyl monoglycol sulfate, were used for the selective extraction of piperine by cell permeabilization of Piper nigrum fruits. Penetration of the hydrotrope molecules into the cellular structures and subsequent cell permeabilization were hypothesized to explain the enhanced extraction rates of aqueous hydrotrope solutions. Hydrotrope molecules, after adsorption on a cell wall, cause disorder in its structure and in the bilayered cell membrane to facilitate the rapid extraction of piperine, The hydrotrope solution showed selective and rapid extraction of piperine from black pepper. The recovered piperine was similar to90% pure and substantially free from oleoresins. The type and nature of the hydrotrope, the hydrotrope concentration, the temperature, and the particle size all had significant effects on the extraction process.