A series of Dy 3+, Sm 3+ co-doped KAlSiO4 phosphor materials were prepared by the high temperature solid phase method. The experimental results show that the doping of a small amount of Dy 3+ and Sm 3+ does not change the crystal structure of KAlSiO4. When KAlSiO4∶1% Dy 3+, w% Sm 3+ is excited at the characteristic excitation wavelength of Dy 3+, there occurs a resonant non-radiative energy transfer from Dy 3+ to Sm 3+ in samples. Meanwhile, the color coordinate shift is very small and there exists a red shift at 528 nm and a blue shift at 713 nm. In contrast, when KAlSiO4∶1.5% Sm 3+, v% Dy 3+ is excited at the characteristic excitation wavelength of Sm 3+, the emission spectrum is very similar to that of KAlSiO4∶1.5% Sm 3+ and there are no characteristic emission peaks of Dy 3+. However, the luminous intensity of Sm 3+ at 651 nm is increased by 6.5 times, which indicates that there does not exist energy return from Sm 3+ to Dy 3+ and the doping of Dy 3+ promotes crystal lattice matching and greatly enhances the luminous intensity of Sm 3+. Theoretical calculations show that the maximum energy transfer efficiency from Dy 3+ to Sm 3+ reaches up to 52% and the energy transfer interaction is electric quadrupole-quadrupole interaction. The color coordinates of phosphors are all around (0.41, 0.51) and located in the yellow-green area. The internal quantum yield under 386 nm excitation gradually increases from 25.8% to 42.6%.