A sequential nucleophilic substitution method produces rotaxanes from anion-sensitive pseudorotaxanes. First, a nucleophilic bulky tertiary aniline interlocks a pseudorotaxane to form a surrogate rotaxane; this unit then functions as a leaving group for a set of bulky nucleophiles, affording rotaxanes with various linking functionalities, along with the bulky aniline recovered in its original form.