In this work the thermal characteristics of cellulose samples with different structure were investigated. The samples were prepared by reacting the cellulose with ethanolic hydroxide solution. Depending on the time of alkaline treatment, the intensity of cellulose transformation differed. Starting from cellulose I structure, with the highest degree of crystallinity, the other samples consisted of mixed structures of cellulose I and II, or were completely transformed to cellulose II structure with the lowest degree of crystallinity. The thermal behaviour of the samples was studied by using a Perkin Elmer TGS-2 and DSC-2 instruments. The kinetic parameters of dehydration and degradation were determined from non-isothermal TG--data (Nitrogen-inert atmosphere and a heating rate of 20 deg/min). The thermal effects of water evolution (heating rate of 80 deg/min) of the cellulose samples were found to depend on the structural characteristics and the crystallinity of the samples. The activation energy and frequency factor were in correlation with the structural changes.