The structures of the first tertiary amide peptide rotaxanes are established in solution by 1H NMRspectroscopy and in the solid state by X-ray crystallography. The hydrogen bonding networks which templatethe rotaxane formation “live on” in nonpolar solvents and strongly influence either the tertiary amide rotamerdistribution or the rate of interconversion between the rotamers depending upon the peptide sequence. Theintercomponent interactionsand their influencescan in appropriate cases be “switched off” by polar solventsleading to “smart” molecular systems which are flexible or adopt several shapes in one environment buttransformed to rigid or single-shaped species in another.