Noninvasive techniques were used for the study in situ of lignification in the maturing cell walls of the maize (Zea mays L.) stem. Within the longitudinal axis of a developing internode all of the stages of lignification can be found. The synthesis of the three types of lignins, p-hydroxyphenylpropane (H), guaiacyl (C), and syringyl (S), was investigated in situ by cross-polarization-magic angle spinning '3C-solid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, and immunocytochemical electron microscopy. The first lignin appearing in the parenchyma is of the G-type, preceeding the incorporation of S nuclei in the later stages. How- Lignin is a complex phenyl propanoid polymer, which is integrated into the wall framework of vascular plant cells. This polymer is complex and heterogeneous with respect to the relative proportions of its three constituting monolignol units (Higuchi, 1990). Variations in lignin composition occur within plant species, tissues, cell types, and also according to developmental stage (Campbell and Sederoff, 1996). The ultrastructural heterogeneity of lignin in secondary walls may be more complex than has so far been demonstrated, because it may be influenced by various factors such as the nature of phenoxy radicals, their steady-