The polymer-supported synthesis of β-mannosides based on the Crich’s protocol has also been studied in the same laboratories. As shown in Scheme 4, diol 17 was first reacted with polystyrylboronic acid (18) to offer the bound donor 19, in which 4,6-O-phenylboronates served as the torsionally disarming protecting group. With that, activation of the thioglycoside 19 was readily achieved, and the coupling reaction with the acceptor alcohol underwent smoothly to provide the bound β-mannoside 20. After removal of the excess reagents and byproducts from the resin, 20 was then treated with aqueous acetone to release 4,6-diol 21. Overall, this is a powerful method for solid-phase synthesis of β-mannosides, which has great potential to be further extended, was established.