Abstract The synthesis and crystal structure of a new one-dimensional mixed-ligand Cu(I) coordination polymer, [(PPh 3) 2Cu 2(μ-I) 2(μ-4,4 ′-bpy)] n (4,4 ′-bpy=4,4 ′-bipydine) are reported. The neutral polymer consists of (PPh 3) 2Cu 2(μ-I) 2(μ-4,4 ′-bpy) units bridged by 4,4 ′-bpy to construct an infinite chain architecture. Crystal data: C 23H 19CuINP, M r=530.80, Triclinic space group ( P 1 , No. 2), a=9.2279(8) Å, b=9.4014(8) Å, c=13.3663(12) Å, α=107.445(2)°, β=106.707(2)°, γ=93.479(2)°, V=1045.8(2) Å 3, D calc=1.686 g m −3, Z=2. The solid state of the complex is luminescent with a peak maximum at 535 nm, upon excitation at 300–400 nm at room temperature. The emission is assigned to Copper(I) to 4,4 ′-bpy charge transfer (MLCT).