A series of Bi3+ Sm3+-codoped Ca14Al10Zn6O35 phosphors were synthesized via conventional high temperature solid-state method. The crystal structure, morphology, photoluminescence and energy transfer mechanism from Bi3+ to Sm3+ were investigated in detail. A broad blue emission band due to P-3(1) -> S-1(0) transition of Be3+ was observed in the Bi3+ single-doped Ca14Al10Zn6O35 sample, the Ca2+ position are verified to be replaced by Bi3+ and the corresponding concentration quenching mechanism was dipole-dipole interaction. The considerable spectral overlap between the broad emission band of Bi3+ around 350-550 nm and the excitation band of Sm3+ supports the energy transfer from Bi3+ to Sm3+. This investigation will contribute to the comprehension of interactions between Bi3+ and Sm3+. These results reveal the potential application of Bi3+, Sm3+ co-doped phosphor in UV light-emitting diodes and artificial light in plant.