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Two new Zn2+‐based metal–organic frameworks (MOFs) based on biphenyl‐2,2′,5,5′‐tetracarboxylic acid, i.e. H4(o,m‐bpta), and N‐donor ligands, namely, poly[[(μ4‐biphenyl‐2,2′,5,5′‐tetracarboxylato)bis{[1,3‐phenylenebis(methylene)]bis(1H‐imidazole)}dizinc(II)] dimethylformamide monosolvate dihydrate], {[Zn2(C16H6O8)(C14H14N4)2]·C3H7NO·2H2O}n or {[Zn2(o,m‐bpta)(1,3‐bimb)2]·C3H7NO·2H2O}n (1) {1,3‐bimb = [1,3‐phenylenebis(methylene)]bis(1H‐imidazole)}, and poly[[(μ4‐biphenyl‐2,2′,5,5′‐tetracarboxylato)bis{[1,4‐phenylenebis(methylene)]bis(1H‐imidazole)}dizinc(II)] monohydrate], {[Zn2(C16H6O8)(C14H14N4)2]·H2O}n or {[Zn2(o,m‐bpta)(1,4‐bimb)2]·H2O}n (2) {1,4‐bimb = [1,4‐phenylenebis(methylene)]bis(1H‐imidazole)}, have been synthesized under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction and powder X‐ray diffraction analysis. Structurally, the (o,m‐bpta)4− ligands are fully deprotonated and combine with Zn2+ ions in μ4‐coordination modes. Complex 1 is a (3,4)‐connected porous network with honeycomb‐like [Zn2(o,m‐bpta)]n sheets formed by 4‐connected (o,m‐bpta)4− ligands. Complex 2 exhibits a (2,4)‐connected network formed by 4‐connected (o,m‐bpta)4− ligands linking Zn2+ ions in left‐handed helical chains. The cis‐configured 1,3‐bimb and 1,4‐bimb ligands bridge Zn2+ ions to form multi‐membered [Zn2(bimb)2] loops. Optically, the complexes show strong fluorescence and display larger red shifts compared to free H4(o,m‐bpta). Complex 2 shows ferroelectric properties due to crystallizing in the C2v polar point group. [ABSTRACT FROM AUTHOR]