Complexation of 1,4‐phenylenebis(methylene) diisonicotinate, L1, with cis‐protected PdII components, [Pd(L′)(NO3)2], in an equimolar ratio yielded binuclear complexes, 1 a–d of [Pd2(L′)2(L1)2](NO3)4 formulation where L′ stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and phenanthroline (phen). The combination of 4,4′‐bipyridine, L2, with the cis‐protected PdII units is known to yield molecular squares, 2 a–d. However, 2 b–d coexist with the corresponding molecular triangles, 3 b–d. Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis‐protected PdII components in DMSO resulted in the D‐shaped heteroligated complexes [Pd2(L′)2(L1)(L2)](NO3)4, 4 a–d. Two units of the D‐shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2(L′)2(L1)(L2)]2(NO3)8, 5 a–d under aqueous conditions. Crystal structures of the macrocycle [Pd2(tmeda)2(L1)(L2)](PF6)4, 4 b′′, and the catenane [Pd2(bpy)2(L1)(L2)]2(NO3)8, 5 c, provide unequivocal support for the proposed molecular architectures.