Degumming is the dominant method to obtain lignocellulosic fibers in the textile industry. Traditionally, wet chemistry methods are used to monitor the evolution of major chemical components during the degumming process. However, these methods lack the ability to provide spatial information for these heterogeneous materials. In this study, besides wet chemistry and scanning electron microscopy (SEM) analysis, a Fourier-transform infrared microspectroscopy (FTIRM) method was employed to monitor the changes in spatial distribution of the main chemical components on the kenaf surface during a steam explosion followed by chemical degum process. The results showed that hemicellulose and lignin were degummed at different rates, and the mechanisms of their degumming are different. The infrared microspectral images revealed the distribution changes of chemical components on the fiber bundle surface during the process, indicating that FTIRM is an effective tool to analyze the degumming process and improve degumming methods.