Laser excitation and x-ray spectroscopy are combined to settle a long-standing question in persistent luminescence. A reversible electron transfer is demonstrated, controlled by light and showing the same kinetics as the persistent luminescence. Exposure to violet light induces charging by oxidation of the excited Eu^{2+} while Dy^{3+} is simultaneously reduced. Oppositely, detrapping of Dy^{2+} occurs at ambient temperature or by infrared illumination, yielding afterglow or optically stimulated luminescence, respectively.