Photofragment spectra of FeS + and NiS + are reported. Analysis of the FeS + spectrum reveals it to arise from a 6Π←6Σ charge-transfer transition, and gives the vibrational frequency, ωe′=295cm−1, and spin–orbit constant, |A|=125cm−1, in the 6Π state. The onset of the NiS + spectrum appears to occur in the middle of a vibrational progression, thus giving a precise measurement of the Ni + –S bond strength, D0(Ni+–S)=238±4kJmol−1. Analysis of the spectrum for vibrational and spin–orbit structure leads to a tentative assignment of a 4Δ ground state and suggests the spectrum is composed of overlapping transitions to two near-degenerate excited electronic states, most likely a 4Π and 4Φ pair.