Silver compound [Ag(Quinox)](ReO4) (I) (Quinox is quinoxaline, C8H6N2) is synthesized, and its crystal structure is determined. The crystals are monoclinic: space group P21/c, a = 7.217(1), b = 15.238(1), c = 9.446(1) Å, β = 93.77(2)°, V = 1036.6(2) Å3, Z = 4, ρcalcd = 3.128 g/cm3. The structure includes cationic polymer chains [Ag(Quinox)]+∞. The Ag+ ion has an almost linear geometry (Ag(1)–N(1) 2.28(1) Å, Ag(1)–N(2) 2.23(1) Å, angle N(1)Ag(1)N(2) 169.0(5)°). The 3D supramolecular structure is formed due to a weak interaction of the oxygen atoms of the ReO4− anions with the silver ions. The compound is luminescent.