The synthesis and spectroscopic characterization of heterometallic porphyrinate derivatives containing rhodiumindium metal-metal bonds are reported. The investigated compounds are represented by the formula [(Porph)-Rhln(Porph')], where Porph and Porph' are OEP, TPP, beta-Cl4TPP, beta-Cl8TPP, or TPyP. UV-Visible spectroscopy of the title complexes confirms the presence of a strong pi-pi interaction between the macrocycles in each derivative and denotes the effect of the nontransition metal in their optical features. For comparison purposes, a new bimetallic complex with a rhodium-thallium metal-metal bond is also presented. According to H-1 and C-13 NMR data, we were able to distinguish two major NMR regions: the endo- between the metal-metal bonded macrocycles and the exo-, which are characteristic features of porphyrinic complexes at very close proximity. X-ray absorption spectroscopy (XAS) structural characterization of Rh-In bond was performed on the [(OEP)Rhln(OEP)] complex, in the fluorescence mode, and we essentially focused on the metal-metal distance determination. Finally, the distance of 2.543(3) Angstrom was deduced from the X-ray structure of a new [(TPP)Rhln(TPyP)] derivative.