A series of NaCa2LuSi2O7F2:xCe(3+),yMn(2+) phosphors are firstly prepared by a high-temperature solid-state reaction technique. The Rietveld refinement analysis confirmed that the obtained phosphors have a pure crystalline phase with cuspidine-group structure. NaCa2LuSi2O7F2:xCe(3+),yMn(2+) phosphors can be efficiently excited by UV light and have two emission bands at about 410 and 600 nm. The luminescent properties of the singly-doped samples reveal that the Ce(3+) ions occupy two different Lu(3+) sites in the host lattice. We observed an efficient energy transfer from the Ce(3+) to Mn(2+) ions. The investigation revealed that the mechanism of the energy transfer was a resonant type via a nonradiative dipole-quadrupole interaction. The hues can be adjusted and white light can be obtained by tuning the concentration of Mn(2+) ions in the codoped phosphors through the energy transfer from the Ce(3+) to Mn(2+) ions, hinting a promising application of NaCa2LuSi2O7F2:xCe(3+),yMn(2+) as a single-component phosphor that can produce white light from UV-based LEDs.