[en] Pyrolysis-gas chromatography/mass spectrometry (Pyrolysis-GC/MS) has been extensively used for characterizing the structural information of various macromolecules such as humic substances, woods, and synthetic polymers. Challinor improved the technique by introducing simultaneous pyrolysis and methylation with tetramethylammonium hydroxide (TMAH). As the technique offers a number of advantages over conventional pyrolysis, it has been used widely for the characterization of a wide variety of macro-organic molecules such as polysaccharides. Thermally assisted hydrolysis and methylation of carbohydrates by TMAH has been investigated. This approach has improved the separation by methylation of acidic functional group. Several researchers have demonstrated that the role of TMAH is not only the methylation of the pyrolysis products but also assisting in bond cleavage. Because TMAH possesses a strong basicity, highly basic conditions are likely to induce a variety of reactions. Pyrolysis technique using TMAH renders polar pyrolysis products volatile enough to be eluted from the GC column by subsequent online methylation