One-dimensional (1-D) chain complexes constructed by metal-metal bonds containing three types of metal species-platinum, rhodium, and copper-have been rationally synthesized and characterized by single-crystal X-ray analyses and physical measurements. The paddlewheel or lantern type complex, [Rh-2(O2CCH3)(4)] (i.e., [Rh-2]), has a vacant sigma* orbital which accepts the electrons from the filled d(z)(2) orbital of cis-[Pt(piam)(2)(NH3)(2)]center dot 2H(2)O (1, i.e. [Pt], where piam = pivalamidate) to afford a tetranuclear complex, [{Rh-2(O2CCH3)(4)}{Pt(piam)(2)(NH3)(2)}(2)]center dot 2H(2)O (2). Compound 2 forms a linear alignment as [Pt]-[Rh-2]-[Pt] with unbridged Rh-Pt bonds, where the oxygen atoms of the piam ligands in the [Pt] are noncoordinated, showing the capability of binding another metal ion. Simply mixing [Rh-2] and the heterometallic trinuclear complex [Pt2Cu(piam)(4)(NH3)(4)](PF6)(2) (3, i.e. [Pt-Cu-Pt]) in a ratio of 1:1 in MeOH, EtOH, or Me2CO affords [{Rh-2(O2CCH3)(4)}{Pt2Cu(piam)(4)(NH3)(4)}](n)(PF6)(2n) (4), [{Rh-2(O2CCH3)(4)}{Pt2Cu(piam)(4)(NH3)(4)}](n)(PF6)(2n) (5), or ({Rh-2(O2CCH3)(4)}{Pt2Cu(piam)(4)(NH3)(4)}](n)(PF6)(2n)center dot 6nMe(2)CO (6), respectively. Compounds 4-6 form infinite chains with the repetition of -{[Rh-2]-[Pt-Cu-Pt]}(n)-, which to our knowledge, are the first examples of heterometallic 1-D chains comprised of three types of metal species with direct metal-metal bonds. The CF3CO2-, ClO4-, and water molecules influence the crystal packing to form an octanuclear complex of [{Rh-2(O2CCH3)(4)}{Pt2Cu(piam)(4)(NH3)(4)}(2)](CF3CO2)(2)(ClO4)(2)center dot 2H(2)O (7) with [Pt-Cu-Pt]-[Rh-2]-[Pt-Cu-Pt] alignment. Considering the crystal structures and X-ray photoelectron spectra (XPS) measurements in 4-7, the oxidation states of the metal atoms are -{[Rh-2(II,II)]-[Pt-II-Cu-II-Pt-II]}(n)- or [Pt-II-Cu-II-Pt-II]-[Rh-2(II,II)]-[(PtII-CuII)-Pt-II], which are unchanged from those in the starting compounds. Electron paramagnetic resonance spectra of 4-7 show axially symmetric spectra with g(parallel to) > g(perpendicular to), indicating that the HOMO (SOMO) is a Cu d(x2-y2) orbital. In 7, the hyperfine coupling in the spectrum indicates that the unpaired spin on Cu is perturbed by the Pt atoms.