A series of decomposed and coalified gymnosperm woods was examined by conventional solid-state 13C nuclear magnetic resonance (NMR) and by dipolar-dephasing NMR techniques. The results of these NMR studies for a histologically related series of samples provide clues as to the nature of codification reactions that lead to the defunctionalization of lignin-derived aromatic structures. These reactions sequentially involve the following: (1) loss of methoxyl carbons from guaiacyl structural units with replacement by hydroxyls and increased condensation; (2) loss of hydroxyls or aryl ethers with replacement by hydrogen as rank increases from lignin to high-volatile bituminous coal; (3) loss of alkyl groups with continued replacement by hydrogen. The dipolar-dephasing data show that the early stages of coalification in samples examined (lignin to lignite) involve a decreasing degree of protonation on aromatic rings and suggest that condensation is significant during coalification at this early stage. An increasing degree of protonation on aromatic rings is observed as the rank of the sample increases from lignite to anthracite.