Lignin samples isolated from Miscanthus giganteus using organosolv processes were treated with vanadium catalysts that were previously developed in our group. We demonstrate that the catalyst with high β-O-4' bond-cleaving activity in dimeric lignin models was also effective in depolymerizing actual lignin. Molecular weight-lowering was evidenced by gel permeation chromatography (GPC), whereas 2D NMR experi- ments showed that β-O-4' linkages were selectively cleaved in the degradation process, just as in the case of lignin models. Monophenolic degradation products were also formed, and the individual molecules were identified and quantified by GC/MS.