SummaryThis paper describes the separation and quantitation of mono-di-and trisaccharides in model solutions. Optimized conditions for identification and determination of common sugar constituents in several natural matrices by GC-MS, from one solution by one injection, are given. Applying a 52 min temperature program to a 30 m capillary column and taking advantage of the stable ratios ofthe syn-and anti oximes eluting either alone or together with one or two other anomers: provides the basis of calculation for co-eluting compounds. Saccharides (5-200 ng), such as fructose, glucose, sucrose, trehalose, cellobiose, maltose, turanose, gentiobiose, palatinose, melibiose, isomaltose, erlose, raffinose, melezitose, maltotriose, panose and isomaltotriose, in the presence of each other in various ratios, have been measured as silyloxime compounds with a reproducibility of < 5 R.S.D. %. The possibility of measuring all these saccharides as their TMS methoximes is also presented.