This paper presents in a comprehensive way the thermal behavior of natural and hot-washed sisal fibers, based on the fundamental components of lignocellulosic materials: cellulose, xylan and lignin. The research highlights the influence exerted on the thermal stability of sisal fibers by other constituents such as non-cellulosic polysaccharides (NCP) and mineral matter. Thermal changes were investigated by thermal X-ray diffraction (TXRD), analyzing the crystallinity index (%Ic) of cellulosic samples, and by simultaneous thermogravimetric and differential thermal analysis coupled with Fourier-transformed infrared spectrometry (TG/DTA-FTIR), which allowed to examine the evolution of the main volatile compounds evolved during the degradation under inert and oxidizing atmospheres. The work demonstrates the potential of this technique to elucidate different steps during the thermal decomposition of sisal, providing extensible results to other lignocellulosic fibers, through the analysis of the evolution of CO2, CO, H2O, CH4, acetic acid, formic acid, methanol, formaldehyde and 2-butanone, and comparing it with the volatile products from pyrolysis of the biomass components. The hydroxyacetaldehyde detected during pyrolysis of sisal is indicative of an alternative route to that of levoglucosan, generated during cellulose pyrolysis. Hot-washing at 75 degrees C mostly extracts non-cellulosic components of low decomposition temperature, and reduces the range of temperature in which sisal decomposition occurs, causing a retard in the pyrolysis stage and increasing Tb-NCP and Tb-CEL, temperatures at the maximum mass loss rate of non-cellulosic polysaccharides and cellulose decompositions, respectively. However, enriching sisal fibers in cellulose produces a decrease of Tb-CEL under an oxidizing atmosphere, and furthermore, a delay of the combustion process, displacing Tb-COM to higher temperatures. The results and findings of the paper would help further understanding of thermal processes where Agave fibers are involved, as the decomposition of their composites. (C) 2014 Elsevier B.V. All rights reserved.