The low-lying electronic states and potential energy curves of XeO and XeS arising from the valence dissociation limits of Xe(S-1) + O(P-3, D-1, and S-1) and Xe(S-1) + S(P-3, D-1, and S-1) and the ion-pair states that correlate with the manifold of Xe+(P-2) + O-(P-2) and Xe+(P-2) + S-(P-2) atomic ion states, respectively, are computed using the complete active space self-consistent field (SCF) followed by multireference single and double configuration interaction methods. The theoretical emission spectra attributed to the ion-pair states of XeO and XeS are reproduced by wave packet propagations and successfully compared to the experimental spectral profile.