Lignocellulose is a promising starting material for bioproducts, ranging from biofuels to specialty chemicals; however, lignocellulose is resistant to enzymatic degradation. Overcoming this resistance is therefore an important priority for the development of the lignocellulosic biorefinery concept. In this work, 1-ethyl-3-methylimidazolium acetate ([emim]Ac) was selected from six ionic liquid candidates for the extraction of lignin from triticale and wheat straw and flax shives. Lignin extractability, composition, and cellulose enzymatic digestibility of the residues after extraction by [emim]Ac were determined at various temperatures (70-150°C) and time intervals (0.5-24 h). The optimal result (52.7% of acid insoluble lignin in triticale straw) was obtained at 150°C after 90 min, yielding >95% cellulose digestibility of the residue. Little cellulose was extracted, and the extracted lignin was recovered by acid precipitation. Selective extraction of lignin by ionic liquids is a potentially efficient technique for the comprehensive utilization of lignocellulose.