A novel heavy fluorous thioglycoside 6 was developed and applied to oligosaccharide synthesis. The fluorous thioglycoside 6 was readily prepared via the corresponding fluorous thiol. Synthesis of the LacdiNPhth derivative was briefly achieved with a single-column chromatographic purification by using a heavy fluorous tag method. Additionally, the fluorous tag was recovered as fluorous alcohol 1 in high yield.