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Four new phenolic dimers and trimers that contain ferulic acid moieties were isolated from the alkaline hydrolyzate of insoluble maize bran fiber and their structures were established by 1D/2D NMR and mass spectrometry. The biological role of one dimer remains unclear whereas the dimeric vanillin-ferulic acid-cross-product probably represents an oxidative degradation product from the corresponding diferulate. Both ferulic acid dehydrotrimers are able to cross-link polysaccharide chains. However, the 5-5/8-O-4(H₂O)-triferulic acid may be a cross-link in its identified structure whereas we assume that the identified 8-O-4/8-5(non-cyclic)-triferulic acid arose from a natural 8-O-4/8-5(cyclic)-triferulate analog during the saponification process.