The ligating properties of alkyl 2-(phenylazo)phenyl thioether 1 (HLR; R = Me, CH2Ph) toward Rh(III) have been examined. A novel hexacoordinated orthometalated rhodium(III) thiolato complex trans-[Rh(L)CI(PPh3)(2)] 5 has been synthesized from 1 and RhCl3 center dot 3H(2)O in the presence of excess PPh3 via in Situ C(Sp(2))-H and C(Sp(3))-S bond scissions, which is the first example for a coordination compound of [L](2-). We were also able to isolate the intermediate organothioether rhodium(III) compound trans-[Rh(L-R)C-2(PPh3)] 6 with 1 equiv of PPh3 relative to both 1 and RhCl3 center dot 3H(2)O in the course of the synthesis of the S-clealkylated product. PPh3 plays a crucial role in the C(Sp3)-S cleavage process. A plausible mechanistic pathway is presented for C-S bond cleavage, and reductive cleavage by singleelectron transfer mechanism is likely to be operative. The electronically and coordinatively saturated thiolato complex 5, indefinitely stable in the solid state, undergoes spontaneous self-dimerization in solution via dissociation of one coordinated PPh3 molecule to afford edge-shared bioctahedral anti-[Rh(L)CI(PPh3)](2) 7 and syn-[Rh(L)Cl(PPh3)](2) 8 isomers. All the synthesized organosulfur rhodium(III) compounds were isolated as both air- and moisture-stable solids and spectroscopically characterized in both solution and solid states. In addition, all the representative members have been authenticated by single-crystal X-ray structure analyses. Availability of the isomeric dimers provides an opportunity to recognize the presence of noncovalent intramolecular "metallochelate-metallochelatd" interaction in the sterically encumbered syn isomer. Unlike other organosulfur rhodium complexes, the monomeric thiolato complex 5 exhibits a fully reversible oxidative wave at 0.82 V vs Ag/AgCl, which is supposed to be primarily centered on the thiolato sulfur atom, and such perception is consistent with the DFT study. Formation of rhodium-bound thiyl radical cation 5 center dot+ by electrochemical oxidation was scrutinized by EPR spectroscopy.