Aiming at developing a novel tool for palaeoclimate research, we recently proposed a new method for determining the oxygen isotope composition of monosaccharides (Zech, M., Glaser, B., 2009. Compound-specific δ ¹⁸O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Communications in Mass Spectrometry 23, 3522-3532). In order to answer the question whether isotope fractionation and oxygen exchange reactions during litter decomposition affect the climatically controlled δ ¹⁸O values of plant derived sugars, such as for instance xylose and arabinose from hemicelluloses, we studied the compound specific δ ¹⁸O values of five different litter species having been decomposed in a field litterbag experiment for 27months.While δ ¹⁸O values of bulk organic matter yielded a systematic ¹⁸O depletion of 3.3‰ (pine) to 4.6‰ (spruce) accompanying total cellulose decomposition of 51% (beech) to 86% (ash), δ ¹⁸O values of individual sugars show no significant trend with time. In addition to the observed absence of isotope fractionation during decomposition, we also rule out ¹⁸O exchange reactions affecting the δ ¹⁸O signature of sugar molecules during diagenetic processes as well as during analytical procedure based on experimental findings and on theoretical biochemical mechanistic considerations. We conclude that our new method may become an analytical tool that elegantly overcomes extraction, purity and hygroscopicity problems of previous ¹⁸O cellulose methods. It furthermore has the potential to be applied to a wide range of climate archives such as tree rings, lacustrine sediments and loess palaeosol sequences.