The spherical and submicron size of Sr₁-xCaxSe:Eu²⁺ phosphors were successfully prepared by ultrasonic spray pyrolysis. The phosphors adopted a cubic structure, and the replacement of Sr²⁺ with Ca²⁺ decreased the lattice parameter. The Sr₁-xCaxSe:Eu²⁺ showed broad and strong excitation under 420-460 nm blue light, and the emission band could be tuned from 565 to 607 nm by increasing the Ca²⁺ ratio in the host lattice. In addition, the doping of Zn²⁺ into Sr²⁺ or Ca²⁺ enhanced the emission intensity with a small red shift due to the change in crystal field strength and nephelauxetic effects. The warm and high CRI of white LED was achieved using blue LED pumped with blending phosphors of 612 nm emitting Ca₀.₉₈Zn₀.₀₂Se:Eu²⁺ and 565 nm emitting YAG. The correlated color temperatures and CRI were 4719.2K, and 86.3, respectively, and an acceptable color variation was also observed at operating currents ranging from 20 to 70 mA.