The luminescence spectroscopy study and the determination of the photophysical parameters for the M-M′-bonded rhodium meso-tetraphenylporphyrin-tin(2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) complex, (TPP)Rh-Sn(Me₆Et₂Cor) 1, was investigated. The emission bands as well as the lifetimes (τ_e) and the quantum yields (Φ_e; at 77 K using 2MeTHF as solvent) were compared with those of (TPP)RhI 2 (TPP = tetraphenylporphyrin) and (Me₆Et₂Cor)SnCl 3 (Me₆Et₂Cor = 2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) which are the two chemical precursors of 1. The energy diagram has been established from the absorption, fluorescence and phosphorescence spectra. The Rh(TPP) and Sn(Me₆Et₂Cor) chromophores are the energy donor (D) and acceptor (A), respectively. The total absence of fluorescence in 1 (while fluorescence is observed in the tin derivative 3) indicates efficient excited state deactivation, presumably due to heavy atom effect and intramolecular energy transfer (ET). The large decreases in τ_P and Φ_P of the Rh(TPP) chromophore going from 2 to 1 indicate a significant intramolecular ET in the triplet states of 1 with an estimated rate ranging between 10⁶ and 10⁸ s⁻¹. Based on the comparison of transfer rates with other related dyads that exhibit similar D-A separations and no M-M′ bond, and for which slower through space ET processes (10²–10³ s⁻¹) operate, a through M-M′ bond ET has been unambiguously assigned to 1.