2-Phosphaphenol (L) forms unusual complexes with copper and gold halides. With CuCl, a dimeric [L₂CuCl]₂ complex is observed with L acting both as η¹-P terminal and μ₂-P bridging ligand and a copper–copper short contact of 2.549 Å. With copper bromide, a distorted infinite chain [L₂CuBr]_n is formed, whereas with copper iodide, the zigzag chain [L₂CuI]_n is observed. The phosphaphenol acts as a terminal ligand coating the CuX molecular wires. With gold chloride, a dimeric [LAuCl]₂ complex is formed, which is held by an aurophilic interaction at 3.132 Å.