The molar mass parameters for arabino-4-O-methylglucuronoxylans, arabinohexenuronoxylans, 4-O-methylglucuronoxylans, hexenuronoxylans, and galactoglucomannans extracted from wood and pulps have been determined. To characterize different types of hemicelluloses, delignified wood (spruce, pine, larch, aspen, and birch) and chemical pulps (unbleached and totally chlorine-free bleached) were extracted with dimethyl sulfoxide (DMSO) or alkaline aqueous solutions. Size exclusion chromatography (SEC) with offline matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-MS) were employed to characterize the molar masses. The hemicellulose extracts were separated by SEC into fractions each containing components with a narrow range of molar masses and the average molar mass of each fraction subsequently determined by MALDI-MS. The molar mass parameters for the hemicelluloses were then calculated on the basis of the SEC distribution curves and MALDI-MS spectra. As expected, in most cases the hemicelluloses extracted from wood (holocellulose) exhibited higher molar masses than did the corresponding hemicelluloses from chemical pulps. The molar mass parameters for hemicelluloses isolated from pulps derived from cooking samples of the same batch of softwood chips decreased in the following order: ASAM pulp > MSSAQ pulp > kraft pulp. The lowest molar masses were demonstrated by the glucuronoxylans extracted from pulps obtained by cooking with acidic sulfite. The xylans from bleached kraft pulp were characterized by molar masses that were only slightly lower than those of the corresponding xylans from unbleached pulp. The xylans extracted into DMSO exhibited somewhat lower molar masses than did the corresponding xylans extracted into alkaline aqueous solutions. In all cases the range of molar masses demonstrated by the hemicelluloses investigated was found to be rather narrow, i.e., the polydispersity index M-w/M-n was found to be approximately 1.1-1.4.