To reveal morphological changes in bamboo constituents induced by delignification and hemicelluloses removal processes, changes in chemical composition and dynamics were examined at molecular- to nano-scales, using scanning electron microscopy images, attenuated total reflection infrared spectra, solid state nuclear magnetic resonance spectra, and relaxation time analysis at multiple hierarchical levels. Boiling removed spherical particles from the parenchymal cells of bamboo, leaving the cells containing water that had infiltrated into the nanostructure composed of carbohydrates and lignin. Treatment of the boiled bamboo with NaClO2 solution removed most of lignin, leaving hemicellulose chains that made the parenchymal cells stretch. In contrast, treatment of the boiled bamboo with NaOH solution removed both hemicellulose and lignin, with the result that parenchymal cells shrank in the cross-section direction. Furthermore, treatment of the delignified bamboo with NaOH solution demolished the parenchymal cells due to complete removal of hemicellulose and lignin. A nanostructural model proposed on the basis of molecular- to nano-scale analyses was consistent with the changes of vascular bundles and parenchymal cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40243.