We report a quantitative synthetic strategy of a [1]rotaxane from a representative pseudo[1]rotaxane. The structure of the [1]rotaxane was characterized by 1H NMR, 13C NMR, 2D NMR, mass spectroscopy, and melting point, and its optimized geometry in CHCl3 by theoretical calculation at the B3LYP/6-31G(D) level using the PCM model matched well with 2D NOESY. This [1]rotaxane proves to be a good catalyst for the Knoevenagel reaction in CHCl3, which follows second order kinetics.