A novel three-dimensional (3D) Zn^II coordination polymer, namely, poly[[[1,4-bis(pyridin-4-yl)benzene](μ₃-3,3′-{[1,3-phenylenebis(methylene)]bis(oxy)}dibenzoato)zinc(II)] 1,4-bis(pyridin-4-yl)benzene], {[Zn(C₂₂H₁₆O₆)(C₁₆H₁₂N₂)]·C₁₆H₁₂N₂} _n or {[Zn(PMBD)(DPB)]·DPB} _n , 1, where H₂PMBD is 3,3′-{[1,3-phenylenebis(methylene)]bis(oxy)}dibenzoic acid and DPB is 1,4-bis(pyridin-4-yl)benzene, has been synthesized by self-assembly using zinc nitrate, a semi-rigid dicarboxylic acid and a nitrogen-containing ligand. The single-crystal X-ray structure determination indicates that 1 possesses an intriguing 3D architecture with a 4-connected uninodal cds topology, which is constructed from dinuclear {Zn₂} clusters and V-shaped PMBD²⁻ linkers. Compound 1 exhibits excellent photocatalytic activity on the degradation of the organic dyes Rhodamine B (RhB), Rhodamine 6G (Rh6G) and Methyl Red (MR).