The main compositional characteristics of rapeseed hulls (RH) and sunflower shells (SS) were examined in terms of non-cellulosic components. The non-sugar fractions were analyzed by solid nuclear magnetic resonance (NMR) and pyrolysis-gas-chromatography/mass spectrometry (Pyr-GC-MS). Unlike SS, RH is a non-lignified biomass. The presence of large amounts of catechol and cresol suggested the presence of phytomelanin in both materials. Sugars accounted for 60% of RH and 45% of SS. Pectic compounds were extracted from the holocellulose of RH with ammonium oxalate or with citric acid, with 17% and 31% yield, respectively. A glucuronoxylan was isolated from the holocellulose of SS in basic conditions with 16% yield.