All doublet and quartet electronic states correlating with the first dissociation channel of SeCl and some Rydberg states are investigated theoretically at the CASSCF/MRCI level of theory using extended basis sets, including the contribution of spin–orbit effects. The similarity of the potential energy curves with those of SeF suggests that spectroscopic constants for the ground (X 2Π) and the first excited quartet (a4Σ−) of SeCl could also be determined via an emission resulting from the reaction of selenium with atomic chlorine. The coupling constant of the ground state at Re is estimated as −1610cm−1. The potential energy curves calculated and the derived spectroscopic constants do not support the interpretation and assignment of the scarce transitions recorded experimentally as due to 2Π–2Π emissions. That the few observed lines might arise from transitions from the state b4∑1/2- to a very high vibrational level of the state a4∑1/2- is an open possibility, however, the number of vibrational states and the calculated ΔG1/2 differ significantly from the reported ones.