Two coordination polymers with 1,4-benzenedicarboxylic acid(H_2BDC) ligand, namely, [Tb_3(BDC)_(4.5)(H_2O)(DMF)_2]_n (1) and [Tb_2(BDC)_3(H_2O)_2(DMF)_2]_n(2), have been synthesized and characterized. Both compounds crystallize in the triclinic system, space group P1. For compound 1, a = 10.8528(5), b = 12.2516(5), c = 16.9031(7) ?, α = 104.462(1), β = 93.659(1), γ = 101.404(1)°, V = 2118.1(2) ?~3, Z = 2, C_(42)H_(34)N_2O_(21)Tb_3, M_r = 1379.47, D_c = 2.163 g/cm~3, μ = 5.045 mm~(-1), F(000) = 1326, the final R = 0.0212 and wR = 0.0570 for 8592 observed reflections with I > 2σ(I). For compound 2, a = 8.547(1), b = 10.170(1), c = 11.192(1) ?, α = 65.531(1), β = 71.886(1), γ = 78.796(1)°, V = 839.2(2) ?~3, Z = 1, C_(30)H_(30)N_2O_(16)Tb_2, M_r = 992.40, D_c = 1.964 g/cm~3, μ = 4.257 mm~(-1), F(000) = 482, the final R = 0.0220 and wR = 0.0649 for 3626 observed reflections with I > 2σ(I). The compounds exhibit different structural topologies depending on the nature of templating agents in the reactions though the templating agents are not incorporated in the final solids. Compound 1 exhibits a three-dimensional(3D) framework based on the rod-shaped terbium-carboxylate building blocks constructed from linear trinuclear Tb3 units. Compound 2 has a 3D framework containing two interpenetrating pcu topological networks based on the 6-connected dinuclear Tb_2 secondary building units. Photoluminescence studies show both compounds exhibit typical Tb(Ⅲ) luminescence emissions. An efficient ligand-to-Tb(Ⅲ) energy transfer is observed in the emission spectra for both compounds. Two coordination polymers with 1,4-benzenedicarboxylic acid (H_2BDC) ligand, namely, Tb_3 (BDC) _ (4.5) (H_2O) (DMF) _2] _n (1) and [Tb_2 (BDC) _3 (H_2O) _2 Both compounds crystallize in the triclinic system, space group P1. For compound 1, a = 10.8528 (5), b = 12.2516 (5), c = 16.9031 (7) , α = 104.462 (1), β = 93.659 (1), γ = 101.404 (1) °, V = 2118.1 (2) ~ 3, Z = 2, C 42 H 34 N 2 O 21 ), The final R = 0.0212 and wR = 0.0570 for 8592 were reflections with I> 2σ A = 8.547 (1), b = 10.170 (1), c = 11.192 (1)?,? = 65.531 (1),? = 71.886 (1),? = 78.796 (1) (V) = 839.2 (2) ~ 3, Z = 1, C 30 H 30 N 2 O 16 Tb 2, M_r = 992.40, D_c = 1.964 g / cm 3, μ = 4.257 mm ~ 1), F (000) = 482, the final R = 0.0220 and wR = 0.0649 for 3626 observed reflections with I> 2σ (I). The compounds exhibit different structural topologies depending on the nature of templatin g agents in the reactions though the templating agents are not incorporated in the final solids. Compound 1 has a three-dimensional (3D) framework based on the rod-shaped terbium-carboxylate building blocks constructed from linear trinuclear Tb3 units. 3D framework containing two interpenetrating pcu topological networks based on the 6-connected dinuclear Tb_2 secondary building units. Photoluminescence studies show both compounds exhibit typical Tb (Ⅲ) luminescence emissions. An efficient ligand-to-Tb (Ⅲ) energy transfer is observed in the emission spectra for both compounds.