Charge compensation of on-site Eu 4f-5d transition that determines the luminescent performance was confirmed with valance band spectrum. Influence of photoelectrons from CaTiO3: Eu to the corresponding luminescent performance was discussed based on the crystal structure, doping level and the relations to their luminescent property. This paper is important to further optimize the luminescent performance for improving the efficiency and reducing the cost in light emitting diode industry. (C) 2016 Elsevier Ltd. All rights reserved.