The efficient synthesis of asymmetrical rotaxanes with different macrocycles and stoppers remains to be a challenged task in the field of supramolecular chemistry. Recently, we report a solvent-free stoppering approach, which allows the efficient interlocking of few macrocycles in the form of [2]rotaxanes. Combining the concept of self-sorting, we plan to construct an asymmetrical [3]rotaxane, in which two macrocycles in different sizes are interlocked efficiently by their corresponding stoppers through a simple solvent-free reaction.