The polysaccharides in the cell walls of dewaxed poplar chips were separated into hemicellulose-lignin complexes (HLC). residual hemicelluloses, and cellulose by extraction with sodium hydroxide at various concentrations. Celluloses (43.9-44.5%), HLC (17.4-21.9%), and residual hemicelluloses (4.3-9.0%) were the major polysaccharide components. Initial extraction of the dewaxed poplar chips with 5% NaOH at 50 degreesC for 4, 6, 8, and 12 hr, and 7.5 and 10% NaOH at 50 degreesC for 6 hr yielded 17.4, 18.2, 18.4, 18.6, 20.3, and 21.9% HLC, respectively. Further extraction of the corresponding alkali-treated and delignified poplar chips with 17.5% NaOH-1% Na2B4O7 . 10H(2)O at 20 degreesC for 2 hr released 9.0, 8.2, 7.9, 7.3, 5.5, and 4.3% residual hemicelluloses, respectively. Xylose was found to be a predominant sugar component (84.3-90.5%) in all of the more linear, acidic, and larger molecular size HLC preparations ((M) over barw, 26.090-40.500 g . mol(-1)). in addition to 4.0-4.8% bound lignin. These lignin molecules were found to be chemically linked to hemicelluloses mainly via syringyl units. On the other hand, all of the residual hemicellulosic fractions contained less xylose (57.3-59.1%) and less uronic acids (4.5-8.9%), but had a higher content of mannose (24.9-26.5%) and glucose (13.3-16.0%). In comparison with the HLC, the residual hemicellulosic fractions had a small molecular size ((M) over bar (w), 18.300-29,730 g . mol(-1)), and had less than half the amount of bound lignin (1.5-1.7%). These lignin molecules were associated with residual hemicelluloses mainly via guaiacyl units. All of the cellulose fractions were relatively free of noncellulosic sugars (contained more than 99.6% glucose), and no considerable degradation of the cellulose was observed under the various separation conditions given.