A novel heterometallic one-dimensional (1-D) chain complex, [{Rh-2(acam)(4)}(3){Pt-2(OPiv)(2)(NH3)(4)}(4)](ClO4)(8) (4, acam = acetamidate, OPiv = pivalate), has been synthesized and characterized by single-crystal X-ray analysis and diffuse reflectance spectroscopy. Complex 4 comprises [Rh-2(acam)(4)] (i.e. [Rh-2]) and [Pt-2(OPiv)(2)(NH3)(4)](ClO4)(2) (i.e. [Pt-2]), where Rh and Pt atoms are axially linked by metal-metal bonds with a repetition of -{[Rh-2]-[Pt-2]-[Rh-2]-[Pt-2]-[Rh-2]-[Pt-2]-[Pt-2]}(n-). All metal oxidation states in 4, determined by structural and X-ray photoelectron spectral analyses, are +2. The unbridged Rh-Pt and Pt-Pt bonds in 4 are supported by multiple hydrogen bonds; the distances of Rh-Pt bonds are relatively longer than those in previously reported 1-D chains despite smaller torsion angles between the Rh and Pt coordination planes. Diffuse reflectance spectra revealed that the electronic structure of 4 has a larger gap between filled and vacant sigma-type orbitals and a smaller gap between a filled pi*(Rh-2) and a vacant sigma-type orbital.