AbstractA new mechanically interlocked molecular linker was prepared by using ring‐closing metathesis (Grubbs I) to clip a [24]crown‐6 ether wheel around an axle containing both Y‐shaped diphenylimidazole and isophthalic acid groups. A metal–organic framework (MOF) material was prepared using this linker and Zn^II ions. Single‐crystal X‐ray diffraction experiments showed that the MOF contains an imidazolium‐based rotaxane linked by dimeric [Zn₂(NO₃)(DEF)] secondary building units (SBUs). Variable‐temperature (VT), ²H solid‐state NMR spectroscopy was used to characterize the motion of the “soft” wheel component around the rigid “hard” lattice of the framework. At higher temperatures (above 150 °C), it was demonstrated that the 24‐membered, macrocyclic ring of the MOF undergoes rapid, thermally driven rotation about the axle inside the voids of the lattice.