The reaction of a trinuclear rhenium sulfide cluster compound Re3S7CI7 with dimethylphenylphosphine and CuX2 (X = Cl or Br) or CuX (X = Cl, Br, or 1) formed tetranuclear cluster complexes [(Ph3P)(2)N][Re-3(CuX)(mu(3)-S)(4)-Cl-6(PMe2Ph)(3)] (X = Cl, Br, or 1). Their solutions have the characteristic intense blue color with visible spectral bands near 600 nm. Single-crystal X-ray structures show that three mu-S atoms in the intermediate trinuclear rhenium complex coordinate to a copper atom, forming elongated tetrahedral structures in which Re-Cu bonding interaction is negligible (Re-Cu distances are 3.50 similar to 3.54 angstrom as compared with Re-Re distances ranging from 2.69 to 2.81 angstrom).