A de-O-benzylation reaction induced by I2-Et3SiH and developed by Iadonisi et al. on mono- and disaccharides was applied to per- or polybenzylated 伪-cyclodextrins to furnish compounds deprotected at position 3 of all sugar units. This methodology allows the straightforward post-functionalisation of the secondary rim of cyclodextrins already functionalised on their primary rim.