Milled wood lignin (MWL) and dioxane lignin (DL) from different morphological regions (nodes and internodes) of Arundo donax reed were subjected to a comprehensive structural characterization by (13)C, (1)H NMR, FTIR, and UV spectroscopies and functional analysis. The permanganate and nitrobenzene oxidation methods were also applied to the in situ lignins. Both node and internode lignins are HGS-type lignins, with a significant amount of H units (including p-coumaric acid type structures). The S/G ratio (1.13-1.32), the weight-average molecular weight (20,400-24,500), the methoxyl group content (0.90-0.98), the phenolic hydroxyl group content (0.23-0.27), and the aliphatic hydroxyl group content (1.00-1.09) are not very different in the lignins from nodes and internodes. However, some structural differences between node and internode lignins were observed. The former has much more phenolic acids (p-coumaric and ferulic), 8.8% in node versus 1.2% in internode and less beta-O-4 (0. 32 and 0.49 per aromatic unit in node and internode, respectively). In situ node lignin is more condensed than internode lignin.