The molecular dynamics of a polyaniline/beta-cyclodextrin inclusion complex (PANT/beta-CD IC) and its relation with optical properties were investigated using high-resolution solid-state C-13 nuclear magnetic resonance (NMR) and optical absorption spectroscopies. UV-vis measurements revealed a pi-pi* absorption peak of a PANI film that had a 10 nm blue-shift by inclusion of beta-CD, indicating that pi-conjugation of PANT was shortened in the IC. Temperature dependent analysis of C-13 NMR spectra and spin-lattice relaxation times (T-1C) revealed that the inclusion induced acceleration of the twisting motion of the PANI chain. Moreover, two twisting motions attributed to different torsional angle modes were observed following Arrhenius plots of T-1C measurements, and the twisting frequency and angle increased above -25 degrees C. These results suggest that the beta-CD inclusion weakens the intermolecular pi-pi interaction and enhances the accompanying twisting motion, consequently leading to a blue-shift of UV-vis absorption.