The formation of pseudorotaxane complexes between cyclotriveratrylene-based molecular container and bipyridinium cation allowed us to synthesize the corresponding [2]rotaxane, in which the guest component penetrated two adjacent 24C8-like openings. Using similar synthetic approach but more sizable aromatic cation as the recognition unit, the guest components in the resulting [2]rotaxane penetrated one 24C8-like opening and its opposite 34-membered ring of the interlocked molecular container. Therefore, two types of guest complexation modes for molecular container were confirmed and the formation of their corresponding rotaxanes was realized.