Ball-milled and enzyme Lignins were extracted with 90 and 50% dioxane-water from 6 days ball-milled wheat straw, and subsequently cellulase-treated straw residues, respectively. The crude lignin preparations were purified using a two-step precipitation method instead of the traditional ether precipitation procedure, and fractionated into pure milled lignin (PML), pure enzyme Lignin (PEL), hemicellulose-rich milled lignin (HRML), lignin-rich enzyme lignin (LREL), and solubilized lignin during enzyme treatment (SLET) fractions. The five lignin fraction were studied using spectroscopic and degradative techniques. The PML and PEL fractions showed very low content of associated polysaccharides (2.36-2.86%). The PML is mainly composed of beta-O-4 ether bonds in the lignin structural units. The less common beta-5 and beta-beta carbon-carbon Linkages are also present. The results obtained also indicated that the lignins in wheat straw cell walls appeared to be very closely associated to p-coumaric and ferulic acid, and glucuronic acid or 4-O-methylglucuronic acid.