There are various methods available to determine the hemicellulosic content of organic material. I use the Van Soest fractionation to determine cellulose, hemicellulose and lignin content of herbaceous lignocellulosic biomass. I don't know if this method can be used for wood.
For wood, you can use the one-step method of Gao et al. 2014
we routinely determine the hemicellulose content of pulps, wood and process water samples by performing acid methanolysis (the published procedure can be found in the reference below). The methanolysis degrades non-cellulosic polysaccharides into their monomeric sugar units and these can then be quantified by GC-analysis using internal standard(s) and a calibration sample (also treated to methanolysis) containing sugars of known concentration.
It works well for neutral sugars, but also for uronic acids such as galacturonic and glucuronic acid (which would be quite challenging to analyze after acid hydrolysis due to degradation!). The method only requires approx. 10 mg of material.
Hardwood hemicellulose is dominated by xylans. In birch, for example, 25-30% of the wood typically consists of O-acetyl-4-O-methylglucuronoxylans.
Sundberg, A., Sundberg, K., Lillandt, C. and Holmbom, B. "Determination of hemicellulose and pectins in wood and pulp fibres by acid methanolysis and gas chromatography", Nord. Pulp Pap. Res. J., 1996, 11(4), 216-219, 226