Eu3+-doped Ba3Al2O6 red phosphors were synthesized by high-temperature solid-state reaction. The crystal structure, morphology and luminescence properties were investigated by XRD, TEM and photoluminescence spectroscopy. The effect of calcination temperature, Eu3+ concentration as well as charge compensators on the luminescence properties was also investigated. Characteristic orange-red emission at 589 nm was detected under 394 nm excitation. The best performance could be derived for the sample calcined at 1450 A degrees C. With the increase of Eu3+ concentration, the emission intensities increased gradually up to the Eu3+ concentration of 12 %. The emission intensities could be enhanced with Li+, Na+ and K+ introduced as charge compensators. The results showed that Ba3Al2O6:Eu3+ phosphors with charge compensator had potential application in the fields of near-UV-excited WLEDs.