The complete transformation from narrow peak emission of Eu3+ to broadband emission of Eu2+ was first realized in La1-xSr2+xAl1-xSixO5:Eu series solutions relying on crystal field engineering and adjustment of synthesis parameters. The original red phosphor La0.97Sr2AlO5:0.03Eu3+peaks at 703 nm originated from 5D0 →7F4 transition of Eu3+ under 395 nm excitation. As the x value regularly increased, Sr2SiO4-type green phosphor La0.17Sr2.8Al0.2Si0.8O5:0.03Eu2+ was synthesized at x = 0.8, which can be efficiently excited by UV/blue light chips. Moreover, when x > 0.975, Sr3SiO5:Eu2+ type broadband orange phosphor Sr2.945Al0.025Si0.975O5:0.03Eu2+ with excellent thermal stability (91.3% peak intensity at 150 °C) was obtained. Variations in the crystal structure, phase, and luminescence properties were studied in detail. We hope this work can provide a reference that solid solution between distinct but structurally related systems is a strategy to explore the possible phosphors for phosphor-converted light-emitting diodes.