The cell wall material of Caragana sinica was fractionated by successive extractions with distilled water at 80 °C for 2 h, 70% ethanol, 70% ethanol containing 1% NaOH, 1 M KOH, 1 M NaOH, 3 M KOH, and 3 M NaOH at 75 °C for 3 h. The sequential treatments resulted in a total dissolution of 86.7% of the original hemicelluloses and 80.1% of the original lignin from dewaxed C. sinica. The current results showed that the four alkali-soluble hemicellulosic preparations, comprising almost 80% xylose of the total neutral sugars, were more linear and acidic, but lower molecular weights (Mw, 28420-55140 g/mol) than the other two organosolv-soluble hemicelluloses (Mw, 57930-96470 g/mol). The 1 M KOH-soluble hemicellulosic fraction was characterized by sugar analysis and 1D, 2D NMR spectroscopy and was found to be composed of a linear (1→4)-β-D-xylopyranosyl main chain with a 4-O-methylglucuronic acid substituting the C-2 position of approximately every eight xylose unit, which is typical of a hardwood acidic 4-O- methylglucuronoxylan (MGX).