A novel and efficient strategy for the synthesis of luminescent polymers bearing metallophilic interactions with unprecedented charge sequences has been designed. For this end suitable basic gold units such as [AuR2](-), bearing perhalophenyl derivatives, and dinuclear acid silver terpyridine species, [Ag-2(terpy)(2)](CF3SO3)(2), have been, chosen. Their combination originates the polymeric derivatives [{AuR2}(2)Ag-2(terpy)(2)](n) (R = C6F5, C6Cl2F3) or [{Au(C6Cl5)(2)}Ag(terpy)](n). The change of the perhalophenyl group in the gold complex modulates the strength in the metallophilic contacts and, consequently, the polymer arrays and luminescent properties. The X-ray diffraction studies of these derivatives revealed that there are polymers with unusual + + = + + = charge sequences for the R = C6F5 and. C6Cl2F3 species, whereas the more classical + = + = disposition was found for the bulkiest C6Cl5 derivative. Their luminescent properties also vary depending on the formation of these polymer arrays, and; time -dependent density functional theory calculations were performed to determine :the origin of the luminescence.