Three Co(II) coordination polymers, namely, {Co(btbb)(0.5)(ndc)(H2O)}(n) (1), {[Co(btbb)(bpdc)]center dot 1.5H(2)O}(n) (2), and {[Co(btbp)(2)(3-npa)]center dot 2H(2)O}(n) (3) (btbb = 1,4-bis(thiabendazole)butane, btbp = 1,3-bis(thiabendazole)propane, H(2)ndc = 2,6-naphthalenedicarboxylic acid, H(2)bpdc = 4,4'-biphenyldicarboxylic acid and 3-H(2)npa = 3-nitro phthalic acid) were synthesized under hydrothermal conditions. Their X-ray crystal structures show that complexes 1 and 2 both have 2D uninodal 3-connected hcb (honeycomb) structures. Complex 1 is further extended into a threefold interpenetrating 3D 4,4-connected mog (moganite) supramolecular architecture with the point symbol of {4.6(4).8}(2){4(2).6(2).8(2)} by O-H center dot center dot center dot O hydrogen bonding interactions. Complex 2 shows a 3D supramolecular framework involving pi center dot center dot center dot pi stacking interactions. Complex 3 features a uninuclear structure, which is further assembled into an ordered 2D hydrogen-bonded-driven pattern with O-H center dot center dot center dot O and O-H center dot center dot center dot N hydrogen bonding interactions. The fluorescence spectra and photocatalytic properties of complexes 1-3 for degradation of methyl orange were investigated.