A series of β-(1→4)-thiooligosaccharide analogs, O -β-D-glucopyranosyl-(1→4)- S -β-D- glucopyranosyl-(1→4)-4-deoxy-4-thio-D-glucopyranose ( 1 : Glc- O -Glc- S -Glc), S -β-D-glucopyranosyl- (1→4)- O -(4-deoxy-4-thio-β-D-glucopyranosyl)-(1→4)-D-glucopyranose ( 2 : Glc- S -Glc- O -Glc), S -β-D-glucopyranosyl-(1→4)-4-deoxy-4-thio-D-glucopyranose ( 3 : Glc- S -Glc), O -β-D-galactopyranosyl-(1→4)- S -β-D-glucopyranosyl-(1→4)-4-deoxy-4-thio-D-glucopyranose ( 4 : Gal- O -Glc- S -Glc) and O -β-D-glucopyranosyl-(1→4)- S -β-D-glucopyranosyl-(1→4)- O - (4-deoxy-4-thio-β-D-glucopyranosyl)-(1→4)-D-glucopyranose ( 5 : Glc- O -Glc- S -Glc- O -Glc), including novel compounds were synthesized for the substrates and/or the inhibitors of cellobiohydrolases for the evaluation of cellulolytic activities. The triflated acceptors were constructed in two reaction steps, regioselective benzoylation and triflation. After S -glycosylation of these triflated acceptors, acyl protecting group was deprotected to yield target compounds. In this way, all target compounds were successfully synthesized in short-step (four reaction steps).