The dark-blue crystal color of {(C(4)H(12)N(2))(2)[Cu(I)I(4)](I(2))}(n), its mixture of I(-), I(3)(-) and linear I(4)(2-) or linear I(5)(-) polyiodide species in a linear channel arrangement, its channel diameter of approximately 5.5 A and the helical arrangement of the hydrogen bonded {(C(4)H(12)N(2))(2)[Cu(I)I(4)]}(+) supramolecular host around the channels agree with the description of the classical, yet structurally elusive, starch-iodine compound.