Grass lignocelluloses, such as those in corn and switchgrass, are a major resource in the emerging cellulose-to-ethanol strategy for biofuels. The potential bioconversion of carbohydrates in this potential resource, however, is limited by the associated aromatic constituents within the grass fiber. These aromatics include both lignins, which are phenylpropanoid units of various types, and low-molecular weight phenolic acids. Structural and chemical studies over the years have identified the location and limitation to fiber degradation imposed by a variety of these aromatic barriers. For example, coniferyl lignin appears to be the most effective limitation to biodegradation, existing in xylem cells of vascular tissues. On the other hand, cell walls with syringyl lignin, e.g., leaf sclerenchyma, are often less recalcitrant. Ferulic and p-coumaric acids that are esterified to hemicellulosic sugars constitute a major limitation to biodegradation in non-lignified cell walls in grass fibers, especially warm season species. Non-chemical methods to improve bioconversion of the lignocelluloses through modification of aromatics include: (1) use of lignin-degrading white rot fungi, (2) pretreatment with phenolic acid esterases, and (3) plant breeding to modify cell wall aromatics. In addition to increased availability of carbohydrates for fermentation, separation and collection of aromatics could provide value-added co-products to improve the economics of bioconversion.