Reactions of 2,3-diphenylquinoxaline (L) with AgClO4· xH2O, AgCF3SO3, AgBF4, AgCF 3CO2 and AgNO3 in equimolar proportions at room temperature yield, respectively, AgL·ClO4·2CH 3OH (1), AgL2·CF3SO3 (2), AgL·BF4·H2O·C2H 5OH (3), AgL2·CF3CO2 (4) and Ag·L·NO3 (5). From X-ray crystallography, complexes 1, 3 and 5 are found to be 1-D hybrid polymers while 2 and 4 are mononuclear. In these five structures, only the nitrate anion is found to be coordinating; other anions are more or less non-coordinating. For the non-coordinating anions, it is concluded that small anions lead to a polymeric cationic complex and larger ones exert a non-proliferating effect in the countercation. In 1 and 3 the polymerization in the complex cation is brought about by bidentate L. But in 5, the anion also becomes a part of the polymeric assembly. The nature of the solvent seems to have little effect on these general observations.