Platinum group metals (PGMs), including rhodium, generated by the fission of (235)U are present in significant quantities within spent nuclear fuel located on power generation sites in the United States, the amount of which is expected to exceed natural reserves by 2030. Yet, spent fuel raffinates are highly acidic media that may result in complex speciation of the PGM. This work provides an understanding of Rh(III) speciation up to 9 M HCl and HNO3, and utilizes a combination of ultraviolet-visible (UV-vis) and capillary zone electrophoresis data, along with computationally predicted thermochemistry and simulated UV-vis spectra to approximate the relative concentrations of potential species in solution as a function of acid concentration. One Rh(III) species, [Rh(NO3)3], is observed under all conditions in HNO3 and for Rh(III) concentrations smaller than 10(-3) M. In contrast, a variety of chloridated Rh(III) species may exist simultaneously in a HCl medium. The species [RhCl2(H2O)4](+) and [RhCl3(H2O)3] are observed in HCl solutions of concentrations ranging from 0 to 1 M; the species [RhCl4(H2O)2](-), [RhCl5(H2O)](2-), and [Rh2Cl9](3-) are observed between 2 and 9 M HCl.