Complexes of the general composition RhIII(phpy)2(S∪E) with phpy− = 2-(2-pyridyl)phenyl and S∪E− = diethyldithiocarbamate, 2-pyridinethiolate and 2-quinolinethiolate were prepared and characterized. The complexes with S∪E− = diethyldithiocarbamate and 2-pyridinethiolate show a low-temperature luminescence which originates from a phpy ππ∗ intraligand triplet. For the complex with S∪E− = 2-quinolinethiolate (or thiooxinate) the lowest-energy excited state is of the quinolinethiolate intraligand type. This complex displays a fluorescence as well as a phosphorescence under ambient conditions