AbstractCell wall‐linked phenolics were investigated in maize internodes located at three positions of the stem (top‐middle‐bottom). While the lignin content did not change drastically with position, the amount of cell wall‐ester linked p‐coumaric acid sharply increased from the top to the bottom internodes of the stem. Conversely, the saponified ferulic acid content remained relatively unchanged along the stem. Moreover, the highest syringyl content of the β‐O‐4‐lignin structures was found in the basal (most mature) internode. Therefore, enhanced p‐coumaric esterification of the cell wall and preferential deposition of syringyl units in the lignin polymer might indicate an extended maturity stage of the cell wall of maize internodes. The bm3 mutation in the three maize hybrids is expressed by lignin reduction and ester‐bound p‐coumaric decrease in the mutant lines. Furthermore, all bm3 hybrids synthesised lignin polymers which were characterised by a very low S/G molar ratio (0.16‐0.43). This ratio originates from the substantial reduction of the syringyl unit content in β‐O‐4‐lignin structures compared with the normal lignin. The occurrence in the same range of the 5‐hydroxyguaiacyl unit in bm3 lignin from each type of hybrids was noteworthy, demonstrating the high heritability of the bm3 mutation at the molecular level. The alkaline solubility of lignin was greater for the three mutant lines compared to the normal cultivars. Furthermore, the alkali‐labile fraction of lignin of both normal and mutant lines had a monomeric composition which was consistent with the non‐condensed structures of in‐situ lignin.