We have recently developed a series of arsenic ligands based on practical synthetic strategies. Herein, three kinds of bidentate arsenic ligands with rigid linkers were selected to construct dinuclear rhombic copper(I) iodide (CuI) complexes, whose structures were analyzed by X-ray crystallography. They had sufficient solubility in organic solvents, and it was confirmed that their coordination forms were kept in the solutions. Intense solid-state emissions were observed even at room temperature, and the emission colors were varied from yellow to red by the ligands.