A series of Mn4+-activated CaAl2O4 (CAO) compounds were synthesized by co-precipitation to seek a candidate for a red-emitting phosphor to be employed in a white LED. The crystal structure, morphology, and fluorescence properties of the as-obtained phosphors were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL). The deep red luminescence of Mn4+ in CaAl2O4 is reported and discussed. The excitation spectrum exhibited broadband emission between 260 and 550 nm with three peaks dominating at 320 nm due to the transition of 4A24T1. Theemission spectra between 600 to 720 nm displays an overwhelming emission peak at 654 nm owing to the 2E4A2 transition of Mn4+ ion.This research demonstrates the great promise of CaAl2O4:Mn4+ as a commercial red phosphor in warm white LEDs and opens up new avenues for the exploration of novel non-rare-earth red-emitting phosphors.