Solvothermal reactions of AgNO3 with N-1,N-4-bis(5-fluoropyridin-3-yl)succinamide (bfps) in MeCN afforded the one-dimensional cationic coordination polymer {[Ag(bfps)]NO3}(n) (1). Upon treatment of 1 with the anionic azo dye orange II (NaOII) in aqueous solution, the NO3- anions of 1 could be gradually exchanged by the anions via an anion-exchange process. The resulting OII- anion-exchanged products {[Ag(bfps)](NO3)(0.85)(OII)(0.15)}(n) (2) and {[Ag(bfps)](NO3)(0.1)(OII)(0.9)}(n) (3) were formed by different molar ratios of 1 and the newly formed phase "{[Ag(bfps)]-(OII)}(n)" (4), confirmed by PXRD patterns. Relative to those of the precursors 1 and NaOII, complexes 2 and 3 demonstrated enlarged photocurrent responses and reduced dielectric constants and dielectric losses, which could be correlated with the OII- contents in their structures. Complex 3 acquired a stable anodic photocurrent of 12.06 mu A, which was 4.9 times higher than that of 1. The dielectric constant (epsilon(r) = 4.2) and dielectric loss (0.002) of 3 were nearly frequency independent in the range from 1 to 10(6) Hz. The results provide an interesting insight into the rational assembly of CP-dye complexes and their tunable optoelectronic applications.