A mechanism of persistent luminescence that was proposed in 1996 for SrAl2O4:Eu2+;Dy3+ has been widely adopted to explain afterglow in many Eu2+ and Dy3+ codoped aluminates and silicates. The mechanism involves the thermally activated release of a hole from Eu2+ in its excited 5d state to the valence band which is subsequently trapped by Dy3+. In this work the location of the lanthanide energy levels relative to the valence and conduction band of various compounds is presented. It is shown that the mechanism of persistent luminescence cannot be correct. An alternative model that involves the ionization of the 5d electron to conduction band states and subsequent trapping by Dy3+ is proposed. The level schemes are consistent, both qualitatively and quantitatively, with many observations regarding persistent luminescence. They also provide insight into the mechanism of thermal quenching of Eu2+ 5d-4f emission. (c) 2005 The Electrochemical Society. All rights reserved.