he structure, mobility, and properties of crosslinked starch materials of various compositions were investigated with FTIR and NMR spectroscopy, and relaxation time measurements were taken with cross-polarization/magic-angle-spinning (CP-MAS) and magic-angle-spinning (MAS) spectroscopy. Characterization by Fourier transform infrared spectroscopy confirmed the crosslinking reaction. The CP-MAS and MAS spectra allowed the assignment of the principal 13C signals. The molecular mobility of these polysaccharides was analyzed in terms of the cross-relaxation time between the protons and carbons, the 1H spin-lattice relaxation time in the rotating frame, and the 1H longitudinal spin-lattice relaxation time. Relaxation studies showed that increasing the crosslinking degree increased the amorphous content, and the material became rigid as an increasing number of covalent bonds in the polymer network reduced mobility. The values of the spin-lattice relaxation in the rotating frame reflected the homogeneous nature of the materials. The correlation between the crosslinking degree, structure, and mobility and the sorption properties of these sorbents was examined.