We reportabinitiocalculations on the electronic states of KrF arising from the Kr+F, Kr++F−, and Kr*+F separated atom limits. We conclude, in agreement with earlier assignments, that the observed laser transition isC(1/2) ‐X(1/2) (5.15 eV calculated, 5.00 eV observed). The calculated lifetime of theC(1/2) state is 6.5 ns. The ionic2&Pgr; state was found to lie close to the ionic2&Sgr;+state.