Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: Studies on the glass transition temperature (Tg) of chitosan are difficult to pursue because of the difficulty in sample preparation and the hydroscopicity of samples. There are a few works concerning this principal relaxation of chitosan. Among them, several quite different values (150℃, 161℃, and 203℃) have been reported. In this paper, the Tg of chitosan (140～150℃) was determined by means of four techniques, namely, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermally simulated current spectroscopy (TSC), and dilatometry (DIL). DSC measurement has been assumed not to be sensitive enough to detect the relaxation temperature of polysaccharides. We propose a new method to improve the sensitivity of the DSC measurement. After a physical aging treatment of samples, the transition in DSC traces became much more distinct because of the enthalpy relaxation. This technique was also used to distinguish the Tg from other relaxations. The Tg of chitosan with different degree of deacetylation (D.D.) was examined by DSC. No influence of D.D. on Tg was found.