CaAl 2 O 4 :Eu 3+ , R + (R=Li + , Na + , K + ) red phosphors were synthesized by solid state reaction method. X-ray diffraction (XRD) and photoluminescence (PL) were employed to characterize their structural and luminescent properties. It was found that the optimal sintering temperature and sintering time were 1200 °C and 4 h, respectively. The optimal concentration of doped Eu 3+ was 3 mol.%. Furthermore, under ultraviolet excitation with a wavelength of 254 nm, these samples showed red luminescence which were probably attributed to the transitions from 5 D 0 excited state to 7 F J (J=0–4) ground states of Eu 3+ ions. The feature and the high intensity of hypersensitive transition from 5 D 0 → 7 F 2 indicated that Eu 3+ preferred to occupy a low symmetry site. The incorporation of alkali metal ions greatly enhanced the luminescence intensity probably due to the influence of charge compensation of alkali metal ions.