CaZr4P4O24:Eu orthophosphate phosphor was synthesized by traditional solid state reaction in air atmosphere. The relationship between the host structure and the characteristic luminescence properties was discussed detailedly. When irradiate the sample under 365 nm UV lamp, intense green emission was observed due to the strong self-reduction process of Eu ions. The oxidation states of Eu ions were identified by muti-method approaches, including photoluminescence spectra, fluorescence lifetimes, Electron spin resonance (ESR) spectroscopy and X-ray photoelectron spectroscopy analysis (XPS). The self-reduction process was controlled by adding the charge compensator Li2CO3 and the self-reduction mechanism was further investigated. (C) 2013 Elsevier Ltd. All rights reserved.