Selective protection for the individual hydroxyl groups of methyl (phenyl 3-deoxy-2-thio-β-D-glycero-D-galacto-2-nonulopyranosid)onate (2) was examined. The 4-, 5-, and 7-hydroxyl groups of methyl (phenyl 3-deoxy-8,9-O-isopropylidene-2-thio-β-D-glycero-D-galacto-2-nonulopyranosid)onate (3) were found selectively to be protected byt-butyldimethylsilyl, methoxymethyl, and benzoyl groups, respectively. In order to obtain the 8- and 9-hydroxyl derivatives selectively, methyl (phenyl 4,5,7-tri-O-acetyl-9-O-t-butyldimethylsilyl-3-deoxy-2-thio-β-D-glycero-D-galacto-2-nonulopyranosid)onate (12) and methyl (phenyl 4,5,7,8-tetra-O-benzyl-9-O-triphenylmethyl-3-deoxy-2-thio-β-D-glycero-D-galacto-2-nonulopyranosid)onate (19) were prepared in moderate yields.