A series of Bi3+, Eu3+ co-activated NaY9Si6O26 (NYSO) powders were prepared by solid-state reaction for the propose of W-LED. The spectral characteristics and occupancies in NYSO lattice for Bi3+, Eu3+ ions were investigated systematically with the help of their excitation spectra, emission spectra, decay curves, X-ray powder diffraction (XRD) and Rietveld method. Bi3+ ions in NYSO phosphors show multiple excitation bands, indicating that there are several various luminescent centers of Bi3+ owing to different occupancies in NYSO lattice. Tunable/white light emission can be obtained by adjusting the doping concentrations of Bi3+ and Eu3+ and changing the wavelength of exciting lights. The quantum yields (QY) of NYSO: 0.008Bi3+, 0.03Eu3+ was measured to be ∼87% under 333 nm excitation. Additionally, the luminous intensity of NYSO: Bi3+, Eu3+ at the ambient temperature of 448 K holds still above 76% of that at 298 K from the temperature dependent spectra, and the analysis of electroluminescence spectrum was also carried out. The results indicate that the Bi3+, Eu3+ co-doped NYSO phosphors have an excellent application prospect in W-LED devices.