The product distribution of the iodine-catalyzed methyl glycosidation of four pentoses (D-ribose, D-arabinose, D-xylose, and D-lyxose) and two 6-deoxyhexoses (L-rhamnose, and D-fucose) was studied by HPLC using an APS column (dihydrogen sulphate form) with different acetonitrile-water mobile phases. In agreement with earlier results, a temperature dependent on-column isomerization was observed for all the investigated aldoses, except for ribose. The first-eluted furanosides were followed by pyranosides, and the free sugars were eluted last with the highest retention volumes.