Bis-azolium salts with one azolium capping a perbenzylated α-cyclodextrin have been designed to generate Janus-type bimetallic complexes with various combinations of copper, silver, gold or palladium salts. Encapsulation of one metal center inside the cavity allowed (trans)metalation and oxidation reactions to be controlled at selected positions. In particular, it was possible to oxidize AuI into AuIII selectively on the position outside the cavity of the cyclodextrin on the bis-AuI Janus complex.