Three coordination polymers, [Zn(HL)(phen)(H2O)]n (1), [Zn1.5(L)(4, 4′‐bpy)1.5]n·4nH2O (2), and [Zn2(HL)2(bib)2]n·2nH2O (3), were assembled from the asymmetric semi‐rigid V‐shaped tricarboxylate ligand 4‐(2‐carboxy‐phenoxy)‐isophthalic acid (H3L) with 1, 10‐phenanthroline (phen), 4, 4′‐bipyridine(4, 4′‐bpy) and 1, 4‐bis (imidazol‐1‐yl) benzene (bib) as auxiliary ligands. Complex 1 features a one‐dimensional (1D) double‐looped chain, which is further extended into a 2D supramolecular layer via two kinds of hydrogen‐bonding interactions. Complex 2 exhibits a complicated 3D framework, which can be rationalized as a (3, 4,4)‐connected trinodal net with a unique (4·8·10) (4·8·10·123) (82·122·14·16) topology. Complex 3 has a two‐dimensional (2D) (4, 4) layer formed by the {Zn2} dinuclear SUBs and the bib ligands. The structural and topological differences of the three complexes indicate that the N‐containing auxiliary ligands play important roles in the formation of the final framework structures. In addition, complexes 1–3 were characterized by elemental analysis, IR spectroscopy, and X‐ray powder diffraction. The thermal behaviors and luminescent properties of complexes 1–3 were also investigated in detail.