I. Abstract Most of the terrestrial carbon is stored in the soil with forest soils containing 40-70% of all soil carbon. Therefore knowledge of SOM composition and decomposition in forest soils is crucial to identify natural sinks of carbon and enhance carbon sequestration, as a way to mitigate climate change. The aims of this project were (I) to study soil organic matter (SOM) under coniferous and deciduous forests, (II) to see how SOM is influenced by substrate type, (III) to search for relationships between environment, species and SOM chemistry in forests of the temperate climate zone and (IV) to present data on the effectiveness of both deciduous and coniferous forests to sequester carbon. In the Gaume (Belgium) and Mullerthal (Luxembourg) study areas, deciduous forests have been partly converted to coniferous forests, often monocultures of spruce (Picea abies). Soil, vegetation and litter samples were taken from adjacent coniferous and deciduous forest plots. Those twin plots were located on different geological substrates. Thermally assisted hydrolysis and methylation (THM) with unlabelled tetra methyl ammonium hydroxide (TMAH) combined with GC/MS was used to analyse lignin, cutin and suberin. The lignin S/G ratio was used as a source proxy and the Ac/AlG and ΓG ratio were used as indicators of lignin decomposition. Cutin and suberin derivatives were used to analyse which part of the SOM originated from above ground biomass (cutin) and which part from below ground biomass (suberin). In addition SOC and FFC stocks were determined. The S/G ratio shows that a different litter input of either needles or deciduous leaves, creates a different SOM composition. Moreover in the Gaume there is a signal of former deciduous forest in the deeper soil layers under the current spruce plantations, suggesting a different vegetation history in both study areas. Geological substrate had a large influence on soil pH and thereby also on soil fertility and SOM composition and decomposition. In both the Gaume and Mullerthal, lignin is more decomposed in the coniferous forest soils than in the deciduous forest soils due to faster decomposition of SOM under more acid conditions. In both study areas, lignin is preferentially decomposed with depth, which is in line with the current dogma that lignin turns over faster than the bulk SOM. The higher suberin yield found for the sandy substrate group, with lower pH, compared with the loamy substrate group in the Mullerthal, supports the hypothesis that at a low pH, root input becomes more important, because of a lack of bioturbation. Substrate is a more important factor for carbon sequestration than forest type. SOC stocks are higher on a marl or limestone substrate than on a sandy substrate. This study supports the assertion by Vancampenhout et al. (2010) that vegetation, through litter input, is a very important determining factor of the extractable SOM composition in maritime temperate forests when climatic conditions are comparable. However in addition this study also highlights the important role of substrate.