Two protocols based on Cu(I) template synthesis and “click” reactions for the synthesis of functionalized [2]catenanes are described. A straightforward procedure, involving high dilution conditions at high temperatures (70 °C), affords [2]catenanes bearing two identical peripheral groups in high yields. For the preparation of non-symmetrically functionalized [2]catenanes, a second milder and simpler protocol was developed, generalizing and extending the method. The introduction of peripheral functional groups into the catenane structure opens up possibilities of using [2]catenanes as building blocks for preparation of even more complex structures.