Monovalent Rh was installed into the group 13 metallatranes, M[N(o-(NCH2P(iPr)2)C6H4)3] (where M = Al and Ga, abbreviated as ML) to generate Rh → M bonds in the parent complexes, Cl–RhAlL (1-Cl) and Cl–RhGaL (2-Cl). The electron-withdrawing nature of the group 13 metalloids was probed by cyclic voltammetry, and Rh–Ga was found to be more electron-deficient than Rh–Al (Epc = −2.07 and −1.95 V vs. Fc+/Fc for 1-Cl and 2-Cl, respectively). Both 1-Cl and 2-Cl were further functionalized through metathesis reactions using MeLi to generate 1-CH3 and 2-CH3, respectively, or using LiHBEt3 to form 1-H and 2-H, respectively. The solid-state structures of all Rh–M bimetallics feature Rh–M bond lengths that are less than the sum of the covalent radii of Rh and M (Rh–M: 2.50–2.54 Å for 1-X and 2.49–2.46 Å for 2-X, where X = Cl, CH3, and H). In the Rh–M structures, the Rh center is distorted from square pyramidal geometry due to steric interactions between X and the isopropyl substituents of L. Finally, all the Rh–M bimetallics exhibit fluxionality that involves phosphine exchange. Of note, the two phosphines cis to the X ligand become inequivalent at low temperature. The activation barrier to exchange these two phosphine donors is: 14.9, 14.2, 10.9, and 11.5 kcal mol−1 for 1-Cl, 2-Cl, 1-H, and 2-H, respectively. The activation barriers for 1-CH3 and 2-CH3 are both >15.2 kcal mol−1. At high temperature, 2-Cl was also found to exchange all three phosphine donors. Mechanisms for the different types of phosphine exchange are proposed.