Rare-earth (RE = Eu, Dy, Tb, and Ce) ion doped core and core–shell LaPO4 phosphors were synthesized to elucidate the effect of spatial distribution of dopants on the emission spectra. The core–shell architecture was designed as a single particle that can be excited by a single wavelength and yield a balanced white light appearance with long emission lifetimes. Specifically, a multishell architecture was employed to separate the Eu3+ and Tb3+ within the phosphor to circumvent the energy transfer between them, passivate the surface quenching sites, and control Ce3+ doping to sensitize other RE ions. To assess the effectiveness of these core–shell phosphors, the International Commission on Illumination (CIE) coordinates and luminescence lifetimes are quantified as the figures of merit. The Eu3+:LaPO4|Ce3+,Dy3+:LaPO4|Tb3+:LaPO4 layering resulted in CIE coordinates of (0.34, 0.35) using 365 nm excitation, nearly at center of the white light regime at (0.35, 0.35). Finally, the emission lifetimes were measured to be 0.85, 4.34, and 3.26 ms and resulted in a total increase of 31, 36, and 16% over the RE3+:LaPO4 reference phosphors, where RE = Dy, Tb, and Eu, respectively. The synthesized phosphor material has high-quality white light with improved emission lifetimes, suitable for application in white light LED devices.