Dry and hydrated insoluble cyclomaltoheptaose (beta-cyclodextrin, beta-CD) polymers have been investigated by solid state 13C NMR spectroscopy techniques such as cross polarization/magic angle spinning with dipolar decoupling (CP/MAS), magic angle spinning both with (DD-MAS) and without (MAS) dipolar decoupling and CP/MAS dipolar dephasing (dd-CP/MAS) to allow the assignment of the main 13C signals. In the solid state, the presence of water in the samples resulted in a better resolution reflecting increased mobility. Two distinct components (crosslinked beta-CD and polymerized epichlorohydrin) have been found. The molecular mobility of these two components has been analyzed in terms of relaxation parameters such as 13C spin lattice relaxation (T1) and 1H spin lattice relaxation in the rotating frame (T1 rho). The T1 values of the polymers show that the beta-CD trapped inside the polymers does not seem to undergo changes in its mobility whatever the amount of epichlorohydrin. The addition of water to beta-CD significantly increases the T1 values reflecting strong interaction between beta-CD and the solvent. The T1P values obtained reflect the homogeneous nature of the materials.