The vacuum ultraviolet excited luminescent properties of Eu3+, Tb3+, Dy3+, Sm3+ and Tm3+ in the matrices of Ca4Y6(SiO4)6O were investigated. The bands at about 173nm in the vacuum ultraviolet excited spectra were attributed to host lattice absorption of the matrix Ca4Y6(SiO4)6O. For Eu3+-doped samples, the O2−→Eu3+ CTB was identified at 258nm. Typical 4f–5d absorption bands in the region of 195–300nm were observed in Tb3+-doped samples. For Dy3+-doped and Sm3+-doped samples, the broad excitation bands consisted of host absorptions, CTB and f–d transition. For Tm3+-doped samples, the O2−→Tm3+ CTB was located at 191nm. About the color purity and emission intensity, Ca4Y6(SiO4)6O:Tb3+ is an attractive candidate of green light PDP phosphor, and Ca4Y6(SiO4)6O:Dy3+ has potential application in the field of mercury-free lamps.