The Sr 4 Al 14 O 25 :M and doped Sr 4 Al 14 O 25 :M+Sm 3+ (M=Mn 4+ , Cr 3+) phosphors were synthesized by a solid-state reaction method and their luminescent properties were investigated. The results showed that the co-doping of Sm ions did not change the positions of excitation band and emission band but significantly improved the luminescent properties of Sr 4 Al 14 O 25 :Cr 3+ phosphors; whereas, the emission intensity of Sr 4 Al 14 O 25 :Mn 4+ was reduced remarkably when Sm ions were co-doped. In addtion, a radiative-form energy transfer from Sm 3+ to Cr 3+ was observed for the first time in the Cr, Sm co-doped Sr 4 Al 14 O 25 phosphors. The results indicated that Sm ions could significantly improve the emission intensity of Sr 4 Al 14 O 25 :Cr 3+ , making the Sm 3+ co-doped Sr 4 Al 14 O 25 :Cr 3+ phosphor a promising candidate for the applications in display and solid state lightening.