Ferulate dehydrodimers and the more recently discovered dehydrotrimers play an important role in the cell wall architecture of plant-based foods and forages. High-performance liquid chromatography methods to determine ferulate dimers often lack specificity; methods for trimers did not exist yet. A method for the determination of 11 cell wall-bound ferulate dehydrodimers and -trimers was developed, including the crucial separation of the di/trimers from the often dominating phenolic monomers. Validation parameters for the basic calibration of the dimers and trimers met our acceptance criteria. However, the matrix calibration revealed that lignin-rich matrices lead to problems with precision and accuracy that likely can be addressed by using a more specific detection, that is, mass spectrometric detection, next to improved sample preparation procedures. The method was used to analyze low-lignin fibers from corn, wheat, and rye grains, wild rice, asparagus, and sugar beet. With the exception of wild rice, the 5-5/8-O-4-, 8-O-4/8-O-4-, and 8-8(aryltetralin)/8-O-4-dehydrotrimers were detected in all analyzed samples, however, often in amounts below the limit of quantitation.