Dual‐ligand strategy was used to synthesize three new coordination polymers with the formula as [Cd(HL)(2,2’‐bipy)]n⋅n(H2O) (1), [Cd3(L)2(bib)3(H2O)]n (2), [Zn(HL)(2,2’‐bipy)]n (3) (H3L=biphenyl‐3,4’,5‐tricarboxylic acid, 2,2’‐bipy=2, 2’‐bipyridine, bib=1,4‐bis(imidazol‐1‐yl)butane), which were further structurally characterized by single crystal X‐ray diffraction analyses. Compound 1 features a 1D infinite chain structure and π…π interactions between adjacent 1D chains gives rise to a 2D layer and further O−H…O hydrogen bonding interactions between adjacent 2D layers affords a 3D supramolecular framework. Compound 2 shows a 3D framework with unprecedented (3,4)‐connected topology. Compound 3 features a 2D→3D interdigitated supramolecular framework based on 2D hydrogen‐bonding layers that constructed from 1D infinite chain and interchain O−H…O hydrogen bonding interactions. Luminescence investigations revealed that compound 1 shows interesting tunable luminescence via altering the excitation wavelength, and compound 2–3 show intense unimodal emission luminescence at room temperature.