Abstract: A process is provided herein for the isolation and recovery of .beta.-sitosterol substantially free of .alpha.-sitosterol from the unsaponifiables obtained from crude soap skimmings or from a crude sterol mixture containing .beta.-sitosterol, .alpha.-sitosterol and campesterol. The starting material is treated with a solvent mixture containing an aromatic hydrocarbon, a polar organic solvent having the ability to form hydrogen bonds, and water. The aromatic hydrocarbon can be replaced by a mixture of an aromatic and an aliphatic hydrocarbon. When the starting material is dissolved the reaction product is precipitated, preferably by cooling the solution, whereafter it is separated from the mother liquor. The obtained product is essentially free of .alpha.-sitosterol.