Tip-enhanced photoluminescence (TEPL) measurements are performed with subnanometer spatial resolution on individual molecules decoupled from a metallic substrate by a thin NaCl layer. TEPL spectra reveal progressive fluorescence quenching with decreasing tip-molecule distance when electrons tunneling from the tip of a scanning tunneling microscope are injected at resonance with the molecular states. Rate equations based on a many-body model reveal that the luminescence quenching is due to a progressive population inversion between the ground neutral ( S 0 ) and the ground charge ( D 0 − ) states of the molecule occurring when the current is raised. We demonstrate that the bias voltage and the lateral tip position can be used to gate the molecular emission. Our approach can be applied to any molecular system, providing unprecedented control over the fluorescence of a single molecule. Published by the American Physical Society 2024