Four novel coordination polymers (CPs), {[Zn₂(tbta)(phen)(OH)]·4H₂O}_n (1), {[Zn₄(tbta)₂(bpy)(OH)₂(H₂O)₂]·7H₂O}_n (2), {[Cu₂(tbta)(phen)(OH)]·4H₂O}_n (3) and [Cu₂(tbta)(phen)₂(OH)]_n (4) (H₃tbta = 1-(triazol-1-yl)-2,4,6-benzene tricarboxylic acid; bpy = 4,4′-bipyridine; phen = 1,10-phenanthroline), were synthesized and characterized by elemental analyses, FT-IR spectroscopy, and single-crystal X-ray diffraction analyses. CP 1 shows a 2D bilayer network structure based on binuclear Zn^II units and (tbta)³⁻ ligands, which are arranged in an [ABAB⋯] alternation to form 3D supramolecular structures through π⋯π stacking interactions and hydrogen bonding interactions. Noticeably, CP 2 forms a 3D network structure based on binuclear Zn^II units and (tbta)³⁻ and bpy ligands. Interestingly, the lattice H₂O molecules are joined by strong hydrogen bond interactions generating (H₂O)₁₀ clusters, which make contact with the 2D network to form a 3D supramolecular structure. CPs 3 and 4 have a 2D network structure. In particular, the (tbta)³⁻ ligands in 1–4 adopt four different coordination modes. The thermal stabilities, XRD, UV, and photoluminescence properties of CPs 1–4 were also studied. Remarkably, CP 1 is a highly selective and sensitive bifunctional luminescent sensor towards Cu²⁺ and Cr₂O₇²⁻ ions. Moreover, CPs 3 and 4 exhibit photocatalytic activities for degradation of dyes (MB/MO) under UV light irradiation.