In conclusion, we have presented simple stereochemical analysis to identify the complete set of [2]catenane and [2]rotaxane mechanical stereoisomers and in doing so recognized a new form of rotaxane geometric isomerism. Furthermore, retrosynthetic analysis of the non-canonical type 2 geometric stereogenic unit allowed us to make the link to the planar chiral stereogenic of rotaxanes, which led to the stereoselective synthesis such molecules.