Pure phytosterols are obtained from the tall oil pitch, mainly containing high boiling fatty acid esters, resin acids and the phytosterols. The tall oil pitch is saponified with food-grade caustic soda to hydrolyze phytosterols esters and saponified the fatty acids. The mixture is then neutralized with a food grade mineral acid (such as sulfuric acid, hydrochloric acid or phosphoric acid). Thereafter the aqueous phase is removed and any remaining water is removed by flash evaporation. The residual pitch is distilled in a number of steps to recover the phytosterol fraction. This fraction is finally purified via solvent re-crystallization using food-grade solvents.