Phosphors BaY2 Si3 O10 : Bi3+, Eu3+ were synthesized by solid-state reaction method. Their phases and optical properties were analysed by using X-ray powder diffractionmeter and fluorescence spectrometer, respectively. The photoluminescence excitation (PLE) spectra of BaY2 Si3 O10 : Eu3+ consist of an enhanced broad charge transfer band (CTB) ranged 200～350 nm and a series of f-f narrow absorption band of Eu3+, the 5D0 →7FJ (J = 1 centered at 592 nm orange, J=2 at 615 nm red) transitions of Eu3+ present the typical orange-red emission band. When phosphors were excited by 285 nm light, the spectral overlap of emission band of Bi3+ and excitation spectra of Eu3+ demonstrated the energy transfer from Bi3+ to Eu3+ that positively enhance the orange-red luminescence of Eu3+ in BaY2 Si3 O10 : Eu3+ . The optimized doping is 0.4 mol% for Eu3+ . The critical transfer distance was calculated to be 1.604 nm, and the concentration quenching mechanism was mainly due to the electric quadrapole-quadrapole interactions.