Two new Cu(II)/Co(II) coordination polymer (CPs) namely, [Co2(H2O)2(L)2(2,2′-bipy)2·H2O] (1) and [Cu2(L)2(bbi)] (2) (H2L=3,3′-(1,2-phenylenebis(methyleneoxy)) dibenzoic acid, bbi = 1,1′-(1,4-butanediyl)bis(imidazole), 2,2,’-bipy=2,2,’-bipyridine), have been designed and synthesized. 1 has 1D helical structure built by the connectivity of Co atoms and phenolic-oxygen containing branches of the flexible dicarboxylate linkages, which was further form a 2D supramolecular sheet through the strong π···π stacking interactions and H-bonded interactions. 2 exhibits 2D layer constructed by the double [Cu4L2] chains and anti-conformational bbi ligands. The current results illustrated that the N-donor ligand may play a distinct effect in the formation of these mortifies. The photocatalytic performances to degrade methyl violet (MV) and Rhodamine B (Rh B) under UV irradiation were studied.