We report the reaction condition-dependent copper(I) iodide complexes 1 and 2, derived from a bis(amidoquinoline) ligand (L)¹. The complex 1, {[(Cu₂I₂)L]•DMSO•CH₃CN}_n, isolated from the slow diffusion method shows a 2D network with an infinite stair step shaped Cu_nI_n cluster backbone. However, in ether vapor diffusion method, we isolated the complex 2, {[(CuI)L]•DMSO}_n, which shows an infinite 2D network linked by rhomboid-type Cu₂I₂ clusters. Interestingly, the complex 2 was also obtained under the mechanochemical condition in the presence of three drops of CH₃CN and one drop of DMSO. Furthermore, the complexes 1 and 2 exhibit yellow (λ_em = 550 nm) and orange (λ_em = 590 nm) emission, respectively, via MLCT.