AbstractUnprecedented threading kinetics were revealed between viologen‐based guests and conformationally adaptive oxatub[4]arene. Three representative conformations of oxatub[4]arene are involved in the kinetic and thermodynamic products which follow the opposite orders in their rankings. Consequently, error correction was involved and a complex kinetic process was observed in a simple two‐component system. Moreover, it was found that some viologen‐based guests have much faster threading kinetics than those of DABCO‐based with the same stoppers. This was enabled by an unprecedented threading mechanism in which a tilted conformation of the guests is adopted by involving one linear alkyl group on the 3,5‐dialkoxybenzyl stoppers, the viologen core, and the methylene spacers in the transition states. This new mechanism even allows the viologen‐based guests with the 3,5‐dicetyloxybenzyl stoppers to form a pseudorotaxane with oxatub[4]arene.