Neutralized and nonneutralized chitosan films subject to different thermal treatments were studied by dielectric relaxation spectroscopy from −130 to +150 °C in the frequency range between 20 Hz and 1 MHz. Two main relaxation processes, both arrhenian type, were detected:  process I at temperatures below 0 °C with a mean activation energy of 49 ± 1 kJ mol^-1, which has the characteristics of a secondary relaxation process related with local chain dynamics, and process II observable at higher temperatures with an activation energy of 94 ± 2 kJ mol^-1, correlated with dc conductivity, which is found in dried polysaccharides systems. Process I is always observed in neutralized chitosan, but it is strongly depleted in the wet nonneutralized form. Although the location of process I is independent of NH₂/NH₃⁺ side group, process II deviates to higher temperatures with dryness in both chitosan forms, being located at lower temperatures in nonneutralized chitosan.