A new and environmentally friendly protocol for the conversion of sugar per-acetates into thioglycosides under solvent free and catalytic conditions is presented. The procedure involves heating in the presence of InCl3 and various aryl thiols. For alkyl thioglycoside synthesis, cyclohexane thiol was found to give good results and yield a glycosyl donor with reactivity similar to a thioethyl congener. The established optimum reaction conditions were found to provide the desired thioglycoside products in an easy and highly diastereoselective manner even when conducted on a multigram scale.