Pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) was used to characterize the pericarp fiber of grain samples of 6 spelt (Triticum spelta L.) along with 3 different bread wheats plus 7 spelt–wheat crosses. Absolute amounts of lignin and polysaccaride pyrolysis products were quantified as μg mg−1 of sample using an internal standard method. The pyrolysis fragments ascribed to the polysaccharide fraction were significantly more abundant in spelt whereas wheats contained the highest percentage of lignin-derived pyrolysis fragments. Discriminant analysis differentiated spelt, spelt–wheat crosses and wheat. Thus, among possible options for fiber analysis, PY/GC/MS proved to be a reproducible and reliable analytical tool, which can be easily applied to the screening and characterization of cereal fiber. © 1998 John Wiley & Sons, Ltd.