The first Janus [2]rotaxane 3 has been synthesized by bis-azo coupling of 2-naphthol-3,6-disulfonic acid with a Janus [2]pseudorotaxane 2 prepared by dimerization of 6-O-[(4-aminophenylazo)phenyl]-permethylated α-cyclodextrin 1 and characterized by MALDI-TOF-MS and 1H NMR methods.