Maize stovers collected every 14 days over an 84-day growth period were subjected to high-performance liquid chromatography with electrochemical detector (HPLC-ED) and pyrolysis/gas chromatography/mass spectrometry (PY/ GC/MS) in order to monitor changes in the phenolic composition. Prior to HPLC-ED analyses, ground samples were sequentially extracted with (i) methanol, (ii) 0.1 M sodium hydroxide and (iii) 2 M sodium hydroxide in the presence of nitrobenzene to separate, respectively, free phenolic monomers, alkali-labile phenolic monomers and alkali-resistant lignin. In turn, solution (ii) was treated with alkaline nitrobenzene to obtain (iv) alkali-labile lignin. Pyrolysis was carried out on ground native samples by using a platinum heated filament pyrolyser. Increases in the absolute phenolic concentrations in the residues of 0.1 M sodium hydroxide extraction and in the ratio of alkali-resistant lignin vs total lignin were observed by HPLC-ED during the first 28-42 days of maturation, reaching a steady level in the remaining maturation period. A linear increase of syringyl units vs guaiacyl units was for found the alkali-resistant lignin fraction over the entire period of maturation. Similar trends were showed by PY/GC/MS with regard to relative lignin content and syringyl/guaiacyl ratio. Both techniques showed their usefulness to gauge changes in the phenolic composition during the lignification process.