A single-crystalline defect-less phosphor is desired for efficient luminescence of the therein doped optical activators. In this paper, microsized MgAl2O4:Mn4+ single-crystal phosphors with bright red luminescence were grown in molten LiCI salt at 950 degrees C, for application in blue LED pumped white lighting. By comparing the phosphor formation from various Mg2+- and Al-3(+)- bearing sources, both the template-formation and the dissolution-diffusion processes were evidenced to account for the formation of the microsized MgAl2O4:Mn4+ crystallites. Using nano gamma-Al2O3 as the Al3+-bearing precursor, the uniform MgAl2O4:Mn4+ microcrystallites with a {111} planes-exposed tetragonal bipyramid morphology were obtained. The photoluminescence property was studied at various temperatures, and Mg <-> Al anti-site disorder induced luminescence broadening was discussed. The Mn-4(+ )-> E-2(g) (4)A(2g) transition in MgAl2O4 shows a quite short luminescence wavelength peaking at 651 nm and ultrabroadband emission extending to 850 nm. The luminescence is relatively robust against thermal effect with relatively high thermal quenching temperature of 400 K and activation energy of 0.23 eV. Employing the red-emitting MgAl2O4:Mn4+ crystallites, blue LED pumped white lighting prototypes were fabricated which simulate the solar-like spectrum and show neutral to warm white.