Organic matter, particularly humic substances and lipids, play an important role in soil processes (Stevenson, 1982). Previous studies have shown that lipid fraction from soil contains complex, macromolecular lipids which resemble a protokerogen (Ambles et al., 1991). The reversible incorporation of organic molecules in macromolecular lipids by ester groups was clearly demonstrated (Amblbs et al., 1994). Main of our results suggest that such a tranfer may also occur in humic substances. Moreover, these biomacromolecules can partly escape biodegradation and fossilizate after deposition in aquatic or hydromorphous environments. As a matter of fact, a close relationship could be established with sedimentary organic matter. Despite their geochemical importance, the structure of soil macromolecules remains largely unknown due to their heterogeneity and extreme complexity which render structural information often difficult and controversial. Different analytical techniques must be complementarily used to avoid misinterpretations in structural determination. In this work, the structure of macromolecular lipids, humic acids and insoluble humin present in an acidic anmoor soil sample (dystric histosol) from Plateau de Millevaches (France), where organic matter is accumulating, was studied using selective chemical degradations, pyrolysis and a new preparative TMAH thermochemolysis technique. The original soil sample contained 56% of total organic matter (TOM), based on oven-dried soil. Lipids contributed to 5% of TOM of the samples, fulvic acids to 21% and humic acids to 17%. The most important organic fraction was humin corresponding to 57% of TOM. Complex macromolecular lipids corresponded to 12% of lipids (0.6% of TOM). Hydrolysis of humin and humic acids. Stepwise hydrolysis was applied using a toluene solution of 18-Crown-6/KOH complex. A large part (87%) of the initially insoluble humin became soluble after a first series of hydrolyses. The soluble high molecularweight products thus obtained were still reactive when submitted again to the same conditions (2nd series of hydrolyses). Humic acids showed a lower reactivity. Linear dicarboxylic acids were produced in significant amounts from humin, they were short (mainly C9) in the first series and long even C16-C28 members of plant origin in the second one. Linear C12-C32 monocarboxylic acids and alkanols were freed from humin and humic acids. The short linear fatty acids and alkanols accompanied with isoand anteiso-C15 and C17 members denote a bacterial input while long even components, as well as various aromatic acids, originate from plant. Alkanols appeared as important hydrolysis products from both samples, mainly freed during the first series of experiments in the case of humin. They are C12-C30 n-alkanols with dominant C16, ClS, C20, C22, C24 and C26 members giving evidence for an important bacterial input. The identification of the iso C15 member confirms such a contribution. However, the source of the dominant n-C22 alkanol observed in humin and humic acids is not well explained. The results indicate that esterified aliphatic dicarboxylic acids are implicated in the reticulation of macromolecular chains corresponding to the matrix of humin. The matrix of humin and humic acids is substituted by alkyl chains which correspond to esterified fatty acids and alcohols, and by aromatic acids. These moieties are acting as monosubstituents. It is interesting to note that this model presents a high resemblance with the kerogen of many immature sediments. Thermochemolysis of humin and humic acids. Humic acids and humin were also investigated in their ester and ether groups using a new preparative TMAH thermochemolysis technique which allows the treatment of high quantity of product (~2g). Preparative TMAH thermochemolysis of humin and humic acids yields various hydrocarbons (alkene/ alkane doublets, sterenes, hopenes and hopanes), methyl esters of linear and branched fatty acids, linear dicarboxylic acids, oJ-methoxy fatty acids and 1-methoxyalkanes. In both samples, hydrocarbon distributions are dominated by classical pyrolytic series of Cls to C37 n-alk-l-ene/n-alkane doublets. Various steroids and triterpenoids, C27, C29 A-2 sterenes, C29 stera-