By using alternating-current electrochemical synthesis, crystals of the Cu(I) pi-complexes bis(1-allyl-2-aminopyridinium) di-micro-chloro-bis[chlorocopper(I)], (C(8)H(11)N(2))(2)[Cu(2)Cl(4)] or [H(2)NC(5)H(4)NC(3)H(5)][CuCl(2)], and bis(1-allyl-2-aminopyridinium) di-micro-(chloro/bromo)-bis[(chloro/bromo)copper(I)], (C(8)H(11)N(2))(2)[Cu(2)Br(2.2)Cl(1.8)] or [H(2)NC(5)H(4)NC(3)H(5)][CuBr(1.10)Cl(0.90)], have been obtained and structurally investigated. In each of the isostructural (isomorphous) compounds, the distorted tetrahedral Cu environment involves three halide atoms and the C=C bond of the ligand. Both compounds reside on inversion centres, and the dimeric [Cu(2)X(4).2H(2)NC(5)H(4)NC(3)H(5)] units are bonded into a three-dimensional structure by N-H...X hydrogen bonds. The Br content in the terminal X1 position is much higher than that in the bridged X2 site.