Two types of heterometallic one-dimensional chains, [{Rh-2(acam)(4)}{Pt-2(piam)(2)(NH3)(4)}(2)](n)(CF3SO3)(4n). 2nMeOH (2, where acam = acetamidate, piam = pivalamidate) and [{Rh-2(acam)(4)}{Pt-2(piam)(2)(NH3)(4)}](n)(CF3CO2)(2n). 2nEtOH (3), have been synthesized and characterized by single-crystal X-ray analyses. The chain structures in 2 and 3 are composed of two kinds of dinuclear complexes, [Rh-2(acam)(4)] (i.e., [Rh-2]) and [Pt-2(piam)(2)(NH3)(4)] (i.e., [Pt-2]), where Rh and Pt atoms are axially linked by metal metal bonds. In 2 and 3, each complex is one-dimensionally aligned as -{[Rh-2]-[Pt-2]- [Pt-2]}(n)- or -{[Rh-2]-[Pt-2]}(n)-, respectively, in which different alignments are caused by different isomers of [Pt-2] that are HH (head head) and HT (head tail) orientation of piam ligands and their hydrogen bonding modes. Considering the crystal structures and X-ray photoelectron spectra (XPS) measurements in 2 and 3, the oxidation states of the metal atoms are -{[Rh-2(II,II)]-[Pt-2(II,II)]-[Pt-2(II,II)]}(n)- and -{[Rh-2(II,II)]-{Pt-2(II,II)]}(n)- which are unchanged from those in the starting compounds. The diffuse reflectance spectra show that LUMOs are M-M sigma-type orbitals. The gap between filled and vacant sigma-type orbitals in 3 is narrower than that in 2, and is attributed to the relative higher destabilized filled sigma-type orbitals caused by lower numbers of linking platinum atoms.