The reaction of a C₃-symmetric tridentate ligand, N,N′,N′′-(4,4′,4′′-nitrilotris(4,1-phenylene))triisonicotinamide (L), with various d¹⁰-metal salts of CuI, Cu(SCN), and M(ClO₄)₂ (M = Zn, Cd) led to four metal–organic materials of {[(Cu₂I₂)(L)₂]·4DMF·2MeOH}_n (1), {[Cu(L)₂(NCS)₂]·3DMF}_n (2), and {[M(L)₂(ClO₄)₂]·4EtOH}_n (M = Zn 3 and Cd 4), respectively, which have been isolated and structurally characterized by X-ray diffraction studies. The X-ray analysis revealed that the interlocking of the 1-D double-zigzag chains of 1–4 into the macrocycles of the adjacent chains generates a novel 2-D (1-D → 2-D) polyrotaxane framework. In these 2-D polyrotaxane frameworks, the C₃-symmetric tridentate ligand, L, only adopts a μ₂-bridging mode, and the third arm is free. In addition, 1–4 are all emissive with dual emissions (431–452 and 558–570 nm) in the solid state at room temperature and at 77 K, which are suggested to be due to an intraligand transition of L based on the high similarities in emission energies to that of L.