A highly efficient and mild method for the de-O-benzylation of protected saccharides was developed by transforming terminal benzyl ethers into silyl ethers using Co(2)(CO)(8)-Et(3)SiH under 1 atm of CO. The method was successfully used for the de-O-benzylation of perbenzylated monosaccharides with various anomeric protecting groups, as well as natural disaccharides and trisaccharides such as sucrose, raffinose, and melezitose in good yields (>80%).