The structure of the lignins of sugarcane bagasse and straw was investigated. The lignins were characterized both in situ and in isolated preparations (Milled-Wood Lignin, MWL, and Cellulolytic Lignin, CEL) by Py-GC/MS and 2D-NMR. It was concluded that they are p-hydroxyphenyl-guaiacyl-syringyl lignins with associated pcoumarates and ferulates. 2D-NMR indicated that the main substructures present are β–O–4´-ethers, followed by β–5´ phenylcoumarans and with lower amounts of β–β´ resinols and β–1´ spirodienones.