A blue phosphor was obtained by doping Eu 2+ into a multi-cation host Sr 0.8 Ca 0.2 Al 2 Si 2 O 8 through high temperature solid state reaction. The emission spectra show a continuous red-shift behavior from 413 nm to 435 nm with Eu 2+ concentration increasing. The substitution priority of Eu 2+ in Sr 0.8 Ca 0.2 Al 2 Si 2 O 8 was investigated via x-ray diffraction (XRD) and temperature properties in detail: the Ca 2+ ions are preferentially substituted by Eu 2+ at lower doping, and with the Eu 2+ concentration increasing, the probability of substitution for Sr 2+ is greater than that of replacing Ca 2+ . Accordingly, we propose the underlying method of thermal property to determine the substitution of Eu 2+ in the multi-cation hosts. Moreover, the abnormal increase of emission intensity with increasing temperature was studied by the thermoluminescence spectra. The energy transfer mechanism between the Eu 2+ ions occupying different cation sites was studied by the lifetime decay curves. A series of warm white light emitting diodes were successfully fabricated using the blue phosphors Sr 0.8 Ca 0.2 Al 2 Si 2 O 8 : Eu 2+ with commercial red phosphor (Ca Sr)SiAlN 3 : Eu 2+ and green phosphor (Y Lu) 3 Al 5 O 12 : Ce 3+ , and the luminescent efficiency can reach 45 lm/W.