A series of Ca4-yY6-xO(SiO4)(6): xCe(3+), yEu(2+) samples are synthesized by a high-temperature solid-state method. Under 356nm excitation, Ca4Y6O(SiO4)(6):Ce3+ presents a strong blue emission band at 426nm which are assigned to 4f(0)5d(1)4f(1) transition of Ce3+ ion. Ca4Y6O(SiO4)(6):Eu2+ shows green emission under 380nm radiation excitation, and the peak locates at 527nm which is mainly due to transitions of Eu2+ from 4f(7) ground state to 4f(6)5d(1) excited state. Under 356nm excitation, a remarkable energy transfer from Ce3+ to Eu2+ exists in Ca4Y6O(SiO4)(6), and the result reveals that the mechanism of energy transfer is a resonant type via a nonradiative dipole-dipole interaction. The hues of Ca4Y6O(SiO4)(6):Ce3+, Eu2+ can be adjusted by the energy transfer from Ce3+ to Eu2+ ions, and a white emission can be achieved by tuning the ratio of Ce3+ to Eu2+. The results mean that Ce3+ may be the effective sensitizer for Eu2+-doped Ca4Y6O(SiO4)(6).