We investigate the luminescence of Si supersaturated with S (Si:S) using depth-resolved cathodoluminescence spectroscopy and secondary ion mass spectroscopy as the S concentration is varied over 2 orders of magnitude (1018–1020cm−3). In single-crystalline supersaturated Si:S, we identify strong luminescence from intra-gap states related to Si self-interstitials and a S-related luminescence at 0.85 eV, both of which show a strong dependence on S concentration in the supersaturated regime. Sufficiently high S concentrations in Si (>1020cm−3) result in complete luminescence quenching, which we propose is a consequence of the overlapping of the defect band and conduction band.Engineering and Applied Science