Rotaxanes comprising dibenzo-24-crown-8 and a symmetrical ammonium salt were desymmetrized by N-acylation. The shuttling behavior was investigated in detail. For the N,N-di-n-alkyl-type axle, the propionyl group was necessary to stop shuttling, whereas the acetyl group was bulky enough for the N,N-,N-dibenzyl-type axle. According to the Delta S double dagger term of the shuttling, the N-formyl and N-acetyl rotaxanes with an N,N-di-n-alkyl-type axle showed similar shuttling frequencies at room temperature.