A water soluble [6]catenane consisting of two interlocking [3]catenanes was synthesised in 91% yield using readily accessible precursors. The new strategy features the simultaneous use of orthogonal Cu⁺–phenanthroline and CB[6]–ammonium interactions for preorganising the precursors and the efficient CB[6]-catalysed azide–alkyne cycloaddition as bond forming reactions for ring closing, resulting in high structural complexity and fidelity of the products without compromising interlocking efficiency. A related [4]catenane with three different types of macrocycles was also obtained in good yield.