The apatite compound Ca₄La₆(SiO₄)₄(PO₄)₂O₂ (CLSPO) was explored as the host material for phosphors used in white light-emitting diodes (wLEDs). The crystal structure of the CLSPO host prepared by the solid-state reaction method was investigated with Rietveld refinement. The rare earth ions (Eu³⁺/ Tb³⁺/Ce³⁺, Tb³⁺/Tb³⁺, Mn²⁺) activated CLSPO phosphors were synthesized, and their photoluminescence properties, quantum yields, as well as thermal stabilities, were studied. Under near-ultraviolet excitations, the Eu³⁺ and Tb³⁺-doped CLSPO compounds exhibited red and green emissions with high luminescence efficiencies. Besides, tunable emissions from green to orange were obtained by introducing Mn²⁺ ions into the Tb³⁺-doped CLSPO samples. The results showed that the phosphors studied may have potential applications for wLEDs.