A series of Na2CaSiO4:Sm3+, Eu3+ phosphors is prepared by the high-temperature solid-state reaction method at 1150℃, and their crystal structures, luminescent properties and energy transfer phenomenon influenced by Sm3+ and Eu3+ are studied. The X-ray diffraction results indicate that the samples single-and co-doped with Sm3+ and Eu3+ keep single-phase and no impurity phases are observed. At the excitation wavelength of 404 nm, the Na2CaSiO4:Sm3+ samples emit narrow-band spectral fluorescence with lines composed of peak-to-peak values of 565, 602, 650, 713 nm, which correspond to the electronic transitions of Sm3+ from the ground state level 4G5/2 to 6H5/2, 6H7/2, 6H9/2, and 6H11/2. On the other hand, the Na2CaSiO4:Eu3+ sample exhibits red emission with a peak-to-peak value of 613 nm at the excitation wavelength of 395 nm. The analyses of the spectrum and lifetime of fluorescence show that with the increase of Eu3+ content, the emission intensity of Sm3+ decreases and the emission intensity of Eu3+ increases. Moreover, the lifetime corresponding to Sm3+ at 602 nm decreases gradually. It is indicated that the energy transfers from Sm3+ to Eu3+. The critical distance of energy transfer is 1.36 nm, which is calculated by the concentration quenching method. The energy transfer mechanism is ascribed to the quadrupole-quadrupole interaction. As the Eu3+ doping concentration increases, the transfer efficiency increases to 20.6%. In conclusion, the Na2CaSiO4:Sm3+, Eu3+ phosphors may be used as a red component for white light-emitting diodes.