Three new coordination polymers, [Zn(PBDC)(bbbm)0.5]n (1), [Co(PBDC)(bbbm)]n (2), and [Cd(PBDC)(bbbm)]n (3) were prepared via hydrothermal reactions of different metal(II) nitrates with flexible 1,3‐bis(4‐phenoxy)benzenedicarboxylic acid (H2L) and 1,1‐(1,4‐butanediyl)bis(benzimidazole) ligand. All these complexes were fully characterized by elemental analysis, FT‐IR, thermogravimetric analysis (TGA), powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Structure analyses revealed that complex 1 has a 2D→2D twofold interpenetrating framework simplified by a 4‐connected sql net with point symbol (44.62), whereas complexes 2 and 3 are isostructural and exhibit a 2D→2D twofold interpenetrating framework rationalized as a three‐connected hcb net with point symbol (63). Complexes 1–3 further expand to 3D supramolecular structures through non‐covalent C–H···O interactions. Additionally, the luminescent and magnetic properties of some of these complexes were studied. Complex 3 presents ideal photoluminescent behavior, whereas complex 2 shows antiferromagnetic coupling between the central CoII ions, suggesting its latent application in magnetic material.