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For enhancing the emission intensity and broadening the excitation region of Ba3Eu(PO4)3(BEP), Sm3 is doped as sensitizer in this paper. BEP:Sm3 can produce an obvious red emission at near ultraviolet (n-UV) radiation. An effective energy transfer from Sm3 to Eu3 is proved. The commission international de I’Eclairage (CIE) chromaticity coordinates of BEP:Sm3 locate at red region. When the environment temperature is 150 °C, the emission intensity of BEP:0.10Sm3 is decreased to 76% of the initial one at room temperature, and the activation energy is calculated to be 0.164 eV, which can prove the good thermal stability of BEP:Sm3 . The results indicate that BEP:Sm3 may have potential applications in white light emitting diodes (LEDs).