High-level CASSCF/MRCI calculations with cc-pV5Z basis sets were employed to characterize a manifold of electronic states of the monosulfide cation ScS+ correlating with the three-lowest dissociation channels. The global energetic picture provided by the potential energy curves makes evident a region, especially above 35,000 cm−1, of high density of electronic states that presents a challenge for both experimentalists and computational chemists to assign properly the electronic transitions. For the lowest-lying singlet and triplet states, a whole set of spectroscopic parameters are provided. Additionally, data on dipole moment functions, transition dipole moment functions, radiative transition probabilities and lifetimes are also evaluated for a subset of singlet states, namely, X 1Σ+, B 1Π, C 1Π, G 1Σ+, H 1Π, I 1Π, and J 1Σ+, for which we identified favorable transitions to be investigated experimentally. Our results are sufficiently accurate and reliable to guide and motivate spectroscopists to investigate further this species.