The effect of calcium substitution on the afterglow of tetrastrontium aluminate phosphors (Sr4Al14O25:Eu2+, Dy3+) was investigated. A series of (Sr1-xCax)O⊎nAl2O3:Eu2+(1%), Dy3+(0.5%), with variation of calcium content (x = 0 − 1), were synthesized by a high temperature solid state reaction in a reducing atmosphere. The photoluminescence, persistent luminescence (afterglow), and lumen equivalents of these materials were studied and compared. It turned out that the afterglow properties of the phosphors were strongly dependent on the Sr/Ca ratio. As the Ca content increased, a phase transition and blue shift in emission spectra were observed.