Previously, ionic liquids were found to partially dissolve lignocellulosic biomass. Here, it is reported that the biomass itself does not dissolve directly, but that it is hydrolyzed first before the constituents (cellulose, hemicellulose and lignin) dissolve into the ionic liquid. By addition of an acidic catalyst, this hydrolysis step can take place at milder conditions. Acetic acid is chosen as a suitable acidic catalyst, because it is already present in lignocellulosic biomass in the form of acetyl groups on the hemicellulose. Here, it is shown that acetic acid also works as co-solvent, increasing the solubility of the constituents of lignocellulosic biomass in the ionic liquid. The milder conditions for hydrolysis result in a higher degree of utilization of the lignocellulosic biomass, whereby all constituents can be fully recovered and further processed and the ionic liquid can be reused. (c) 2010 Elsevier B.V. All rights reserved.