A wide range of symmetrical and unsymmetrical glycosyl disulfides is synthesized with focus on the use of α-glycosyl thiols. Oxidation of α-glycosyl thiols with iodine leads to symmetrical α,α-glycosyl disulfides, while unsymmetrical disulfides are readily synthesized from α- and β-glycosyl thiols under the action of DDQ. Thus, glycosyl disulfides containing at least one α-glycosidic linkage are made available.Both symmetrical and unsymmetrical glycosyl disulfides containing α-glycosidic linkages were synthesized readily from the corresponding glycosyl thiols by oxidation with I2 or DDQ.