Four positional isomers of 6(1),6n-di-O-(tert-butyldimethylsilyl)- cyclomalto-octaose (n = 2-5) were prepared by reaction of cyclomalto-octaose (1, cG8) with tert-butyldimethylsilyl chloride in pyridine, and were isolated by high-performance liquid chromatography. The regiochemical determination of those positional isomers was performed by comparison with authentic compounds, prepared from 6(1),6n-di-O-trityl-cG8s (n = 2-5).