Hemicelluloses are a relatively unused renewable resource. One reason is their broad structure variety that makes it hard to understand structure-property relations. In this study arbinoxylan, extracted from barley husk, was chemically modified into hydroxypropyl methyl-, hydroxypropyl- and methyl arabinoxylan. The relationship between structure and phase behavior was investigated by using multivariate analysis. The arabinoxylan ethers were characterized using mid-infrared FTIR spectroscopy and from principal components analysis, PCA, structural or physical variations between samples were visualized. With orthogonal projections to latent structures, OPLS, vibrations specific for arabinoxylan hydroxypropyl and methyl substitutions was assigned. Among the observed differences between chemical derivatives was an intensity change in the water vibration. The differences in hydration were related to clouding phase behavior of the arabinoxylan ethers. This study shows that multivariate analysis methods are useful for finding unexpected and/or hidden features in the polysaccharide structure.