A novel octanuclear Ag(I)(6)-Zn(II)(2) heterometallic aggregate, (NH(4))(2){[Zn(2)(phen)(2)(H(2)O)(4)][Ag(6)(mna)(6)]}·2H(2)O·2CH(3)CH(2)OH (1, H(2)mna = 2-mercaptonicotinic acid, phen = 1,10-phenanthroline), was stepwisely obtained based on a hexanuclear silver(i) metalloligand using a liquid-liquid diffusion method. It is an exceedingly rare example that exhibits interesting temperature dependent photoluminescence behaviors, including gradual changes in energy and intensity upon cooling.