Two new complexes, namely [Cd₂(L)(pycy)(Cl)]·2H₂O (1) and [Cu(HL)(H₂btac)]·2H₂O, have been synthesized by the reaction of the corresponding metal salts with mixed ligands including 1-(1H-imidazol-4-yl)-4- (4H-tetrazol-5-yl)benzene (HL), 2,6-pyridinedicarboxylic acid (H₂pycy) and 1,2,4,5-benzenetetracarboxylic acid (H₄btac), and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and powder X-ray diffraction (PXRD). Complex 1 crystallizes in triclinic, space group P with a = 9.8938(7), b = 10.1662(7), c = 12.4520(8) Å, α = 92.7070(10), β = 108.1310(10), γ = 105.3230(10)°, V = 1136.44(13) ų, Z = 2, C₁₇H₁₂N₇O₆ClCd₂, M_r = 670.59, D_c = 1.960 g/cm³, μ =2.037mm^-1, S = 1.062, F(000) = 648, the final R = 0.0532 and wR = 0.1651 for 12156 observed reflections (I > 2σ(I)). Complex 2 crystallizes in triclinic, space group P with a = 7.3058(8), b = 7.4890(8), c = 10.8937(12) Å, α = 71.3810(10), β = 84.134(2), γ = 65.745(2)°, V = 514.68(10) ų, Z = 1, C₂₀H₁₆CuN₆O₁₀, M_r = 563.94, D_c = 1.819 g/cm³, μ =1.139mm^-1, S = 1.187, F(000) = 287, the final R = 0.0314 and wR = 0.0807 for 3564 observed reflections (I > 2σ(I)). Single-crystal X-ray structural analysis reveals that complex 1 features a trinodal (3,3,4)-connected two-dimensional (2D) net layer with Schläfli symbol (4·6·8)(4·6²·8³)(6²·8) while 2 has a 2D network with 4⁴ sql topology. Moreover, the photoluminescent property of 1 and magnetic property of 2 were also discussed.