In this paper, a new isopolymolybdate anion ［δ-Mo8O26］4--based complex ［Co(bipbc)(δ-Mo8O26)0.5(H2O)3］ (bipbc=4,4′-bis［(4-carboxypyridino)methyl］biphenyl) was synthesized under hydrothermal conditions. The title complex shows a 1D chain, which consists of the cyclic dinuclear cobalt complexes ［Co2(bipbc)2］4+ and ［δ-Mo8O26］4-clusters, and crystallizes in the monoclinic system, space group P21/n with a=1.147 9 (8) nm, b=1.440 9 (11) nm, c=2.082 9 (16) nm, β=93.469(2)°, V=3.438 8(4) nm3, Z=4, Mr=1 129.18, F(000)=2 204, μ=1.979 mm-1, Dc=2.181 mg·m-3, S=1.019, R1=0.056 2, wR2=0.137 7. The investigations on photocatalytic properties show that the title complex has photocatalytic activities toward the degradation of gentian violet (GV) and methylene blue (MB) under visible, even near-infrared and full spectrum light irradiation.