The existing mechanisms proposed to explain the phosphorescence of SrAl2O4:Eu2+,Dy3+ and related phosphors were found to be inconsistent with a number of important experimental and theoretical observations. We formulated a new mechanism of phosphorescence on the basis of the facts that the d orbitals of Eu2+ are located near the conduction band bottom of SrAl2O4, that the Eu2+ concentration decreases during UV excitation, and that trace amounts of Eu3+ are always present in these phosphors. In our mechanism, some Eu2+ ions are oxidized to Eu3+ under UV, and the released electrons are trapped at the oxygen vacancy levels located in the vicinity of the photogenerated Eu3+ cations. The phosphorescence arises from the recombination of these trapped electrons around the photogenerated Eu3+ sites with emission at 520 nm. The codopant Dy3+ enhances the phosphorescence by increasing the number and the depth of electron traps, and the codopant B3+ enhances the phosphorescence by increasing the depth of electron traps. We also probed the origin of another emission at 450 nm of SrAl2O4:Eu2+ that occurs at low temperatures. Our analysis indicates that this emission is caused by a charge transfer from oxygen to Eu3+ cations and is associated with a hole trapping.Read less <