Crystals of the title pi-complex, [Cu4Cl6(C8H11N2)2]n, were obtained by means of alternating-current electrochemical synthesis. The structure consists of infinite copper-chlorine chains to which 1-allyl-3-aminopyridinium moieties are attached via a eta2 Cu-(C=C) interaction. The two independent Cu atoms have distinct coordination environments. One is three-coordinate, surrounded by two chloro ligands and the olefinic bond, whereas the second copper center is surrounded by a tetrahedral arrangement of four Cl atoms. The lower basicity of 3-aminopyridine as compared with 2- and 4-aminopyridine lowers the capacity of the organic ligand for donating to N-H...Cl hydrogen bonds and results in the formation of a large inorganic fragment.