Many research projects require accurate delineation of different secondary succession (SS) stages over large regions/subregions of the Amazon basin. However, the complexity of vegetation stand structure, abundant vegetation species, and the smooth transition between different SS stages make vegetation classification difficult when using traditional approaches such as the maximum likelihood classifier (MLC). Most of the time, classification distinguishes only between forest/non-forest. It has been difficult to accurately distinguish stages of SS. In this paper, a linear mixture model (LMM) approach is applied to classify successional and mature forests using Thematic Mapper (TM) imagery in the Rondônia region of the Brazilian Amazon. Three endmembers (i.e., shade, soil, and green vegetation or GV) were identified based on the image itself and a constrained least-squares solution was used to unmix the image. This study indicates that the LMM approach is a promising method for distinguishing successional and mature forests in the Amazon basin using TM data. It improved vegetation classification accuracy over that of the MLC. Initial, intermediate, and advanced successional and mature forests were classified with overall accuracy of 78.2% using a threshold method on the ratio of shade to GV fractions, a 7.4% increase over the MLC. The GV and shade fractions are sensitive to the change of vegetation stand structures and better capture biophysical structure information.