The decomposition behavior of cotton fibers is examined using thermogravimetric analysis. The effect of the test parameters on the thermal degradation of raw cotton fibers is determined. Focus is given to the influence of water immersion on the thermal behavior of cotton fibers. For less mature fibers a clear difference is noted between the degradation profiles of the water-immersed and untreated samples. On the contrary, only a small change is noted on the degradation profile for more mature fibers after water immersion. The maturity and variations in water-soluble content of the fiber are found to be important factors influencing the thermal behavior of raw cotton fibers. Inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to underpin the effect of water immersion on cotton fibers. This improved understanding for the role of maturity and water soluble constituents in thermal degradation of cotton fibers may lead to develop routes that improve thermal stability and smoldering characteristics of cotton fibers as relevant for future applications.