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In the mixed-valence CuI/CuII coordination polymer, [Cu2Cl3(C20H14N4)]n, the two Cu atoms are bridged to a pair of Cl atoms across a centre of inversion. The monovalent metal atoms is coordinated by a pyridine N atom as well as by three Cl atoms in a tetrahedral CuNCl3 geometry. The divalent metal atom is N,N′,N′′-chelated by the heterocycle, and it exists in a square-pyramidal CuN3Cl2 geometry; the apical site is occupied by the second bridging Cl atom. The bridging modes of the Cl atoms and the heterocycle give rise to the formation of a layered arrangement parallel to (001).