The molecular relaxations behavior of chitosan (CS) films in the wide frequency range of 0.1-3x109 Hz (by using three different impedance analyzers) have been investigated in the temperature range of -100C to 120°C using Dielectric Spectroscopy (DS). Additionally to the low frequency molecular relaxations such as α and β relaxations, for the first time, high frequency (1-3 GHz) relaxation process has been observed in the chitosan films. This relaxation exhibits Arrhenius-type dependence in the temperature range of -100 C to 54°C with negative activation energy -2.7 kJ/mol. At temperatures above 54°C, the activation energy changes from -2.7 kJ/mol to +4.4 kJ/mol. Upon cooling, the activation energy becomes negative again with a value of -1.2 kJ/mol. The bound water between chitosan molecules strongly modifies molecular motion and the relaxation spectrum, giving rise to a new relaxation at the frequency at ca. 1 GHz. In situ FTIR analysis has shown that this relaxation related to the changes in vibration of the –OH, NH and –CO functional groups.