By hydrothermal method, a new coordination polymer [Ag 3 (btc)(dmt)(H 2 O)] n ( 1 ) (H 3 btc = 1,3,5-benzenetricarboxylic acid, dmt = 2,4-diamino-6-methyl-1,3,5-triazine), has been synthesized and structurally characterized by IR spectrum, X-ray single diffraction, and elemental analysis. Compound 1 exhibits a planar 2D layer with 2-nodal (3,4)-connected {4.6 2 } 4 {6 4 .10 2 } topology and further extends to 3D framework through hydrogen bond and Ag…O weak interactions. Moreover, compound 1 displays luminescent property at solid state and holds good catalytic activity toward photocatalytic degradation of RhB.