AbstractA novel three-dimensional (3D) silver(I) coordination polymer, namely [Ag2(dmtrz)2]n(1) (Hdmtrz = 3,5-dimethyl-1H,1,2,4-triazole), was synthesized through diffusion method. 1 was characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 crystallizes in the orthorhombic system,space group Iba2 with a = 12.5026(10), b = 7.6026(6), c = 18.8981(17) Å, V = 1796.3(3) Å3, Z = 6, Mr = 407.98, Dc = 2.263 g·cm-3, μ = 3.252 mm-1, F(000) = 1176, the final R = 0.0304 and wR = 0.0634 for 1310 observed reflections (I > 2σ(I)). In the structure of 1, silver(I) centers are triconnected to dmtrz ligands, forming the (3,3)-connected 3D coordination polymer with a 6.102 topology. The luminescence property of 1 was also studied in solid state at room temperature.