The low-lying electronic transitions and photochemical reactions of a series of [((i)Pr-DAB)Pt(R)(2)] (where the co-ligand R = CH(3), CD(3), adme, neop, neoSi, C(triple bond)C(t)Bu, C(triple bond)CPh, Ph, Mes) compounds were studied using both experimental (electronic absorption and resonance Raman spectroscopy) and theoretical (density functional theory, DFT) techniques. The high-lying filled orbitals were revealed to have a significant co-ligand contribution in the case of alkyl complexes, while this contribution is predominant for the complexes with unsaturated co-ligands. Because the electronic transition removes electron density from the sigma(Pt-C) bond in the former complexes, it is best described as a metal-to-ligand charge transfer transition (MLCT) with partial sigma-bond-to-ligand charge transfer (SBLCT) character. Because the sigma(Pt-C) orbital is not involved in the HOMOs of the latter complexes, the low-lying transitions were characterized as mixed MLCT/L'LCT, where L'LCT stands for ligand-to-ligand charge transfer from the pi system of the unsaturated co-ligand to the pi((i)Pr-DAB) orbital. The alkyl complexes are photoreactive on visible light irradiation with Pt-C bond homolysis as the primary step. The efficiency of the photoreaction increases with increasing sigma donor strength of the alkyl ligand. The absolute quantum yield is quite low. The other complexes are virtually photostable, except when irradiated at relatively high energies.