A series of one‐dimensional (1D) double‐zigzag ({[Zn(papx)2(H2O)2](ClO4)2}n (x=so 1, sc 3, oc 5, and soc 7) and 2D polyrotaxane ([Zn(papx)2(ClO4)2]n (x=so 2, sc 4, oc 6, and soc 8) frameworks are synthesized by the reactions of Zn(ClO4)2 with equimolar amounts of papx (i.e., papso=1/2paps+1/2papo, papsc=1/2paps+1/2papc, papoc=1/2papo+1/2papc, and papsoc=1/3paps+1/3papo+1/3papc; paps=N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl thioether, papo=N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl ether, papc=N,N′‐(methylenedi‐p‐phenylene)bispyridine‐4‐carboxamide). The new frameworks are isolated and characterized by single‐crystal and powder X‐ray diffraction studies, elemental analysis, and 1H NMR spectroscopy. In addition, synthesis and structural characterization of 2D polyrotaxane frameworks of [Cu(papx)2(ClO4)2]n (x=s 9, o 10, and c 11) by the reaction of Cu(ClO4)2 with the respective dipyridylamide ligands are carried out. Based on the PXRD experiments, upon heating, the double‐zigzag frameworks of 1, 3, 5, and 7 undergo structural transformation to give the respective polyrotaxane frameworks of 2, 4, 6, and 8. Moreover, grinding the solid samples of 2, 4, 6, and 8 in the presence of moisture also result in the total conversion back into the double‐zigzag frameworks of 1, 3, 5, and 7, respectively. Remarkably, grinding the solid samples of polyrotaxane frameworks of 9 and 10 in the presence of moisture fails to induce a structural transformation process.