The high‐temperature degumming technology of cotton stalk bark fiber was studied, and the effects of the caustic soda concentration on the constituents, structure, and thermal degradation of the cotton stalk bark fiber were examined. The morphology, structure, and thermal degradation of the cotton stalk bark fiber after high‐temperature degumming were investigated through scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, wide‐angle X‐ray diffraction, and thermogravimetric analysis. The results indicate that the high‐temperature degumming process was effective for removing hemicelluloses and lignin and could improve the thermal stability of the cellulose. The raw and degummed cotton stalk bark fibers both showed the structure of cellulose I, according to the FTIR spectroscopy and X‐ray diffraction results. It was interesting to note that the crystallinity and crystallinity index were related to the caustic soda concentration. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012