Oxidation of the square planar Rh(I) complex [Rh(SPSMe)(PPh3)] (SpS(Me) = 1-methyl-1-P-2,6-bis(diphenylphosphinosulfide)-3,5-(bisphenyl)-phosphini ne) (1) based on mixed SPS-pincer ligand with hexachloroethane yielded the Rh(III) dichloride complex [Rh(SPSMe)(PPh3)Cl-2] (2), which was structurally characterized. The homoleptic Rh(III) complex [Rh(SpS(Me))(2)][Cl] (4) was obtained via the stoichiometric reaction of SPSMe anion (3) with [Rh(tht)(3)Cl-3] (III) = tetrahydrothiophene). Complex 4, which was characterized by X-ray diffraction, was also studied by cyclic voltammetry. Complex 4 can be reversibly reduced at E = -1.16 V (vs SCE) to give the neutral 19-electron Rh(II) complex [Rh(SpSMe)2] (5). Accordingly, complex 5 could be synthesized via chemical reduction of 4 with zinc dust. EPR spectra of complex 5 were obtained after electrochemical or chemical reduction of 4 in THF or CH2Cl2. Hyperfine interaction with two equivalent P-31 nuclei was observed in liquid solution, while an additional coupling with a spin 1/2 nucleus, probably Rh-103, was detected in frozen solution. The P-31 couplings are consistent with DFT calculations that predict a drastic increase in the axial P-S bond lengths when reducing (SpS(Me))(2)Rh(III). In the reduced complex, the unpaired electron is mainly localized in a rhodium d(z)(2) orbital, consistent with the g-anisotropy measured at 100 K.