Bamboo is a gramineous plant widely distributed in China and has great prospects. Normally, local people cut bamboo culm at first year for paper milling or at six years for construction. Understanding lignin changes in bamboo with aging is necessary for better exploring the application of bamboo at different ages and can also promote the application of bamboo more effectively. Based on the previous study, the chemical structure and the lignin content of bamboo at different ages were further explored by FT-IR, GPC, NMR and other chemical methods in this paper. Results showed that the lignin structures of bamboo at different ages were similar with three monomers of S, G and H, but the molecular weight increased with age. Quantitative structure estimation further confirmed that S-type lignin content and S/G ratio of bamboo lignin constantly increased with age.