The one-dimensional polymer, [Cu-2(C8H6N2)(2)(C7H6N2)](2)[Mo8O26] (1), which consists of beta-[Mo8O26](4-) anions linked by quinoxaline and its oxidized product benzimidazole ligands coordinated to binuclear copper(1) fragments, provides the first demonstration that the isolated copper(1) complex under hydrothermal conditions "captures" the reduction product of original starting organonitrogen ligand to form a copper(1)-beta-octamolybdate complex.