Dy3+-doped or Dy3+/Mn4+ co-doped Ca14Al10Zn6O35 phosphors were prepared by the solid-state reaction method. The phosphors were characterized by means of XRD, SEM, luminescence analysis, and thermal stability analysis. The obtained phosphors can be excited efficiently by NUV light and exhibit blue/yellow emission and deep red emission, which result from F-4(9/2) -> H-6(15/2)/F-4(9/2) -> H-6(13/2) transitions of Dy3+ ions and E-2 -> (4)A(2) transition of Mn4+ ions, respectively. The efficient energy transfer from Dy3+ ions to Mn4+ ions was confirmed, which was realized via the electric dipole-dipole interaction. The thermal quenching temperature of the phosphors is higher than 463 K, indicating that the phosphors have an excellent thermal stability. The temperature-induced electron population variation in the vibrational states caused the different influence on the emission intensity of Stokes and anti-Stokes sidebands of Mn4+ ions. By adding Na+ ion as a charge compensator and changing its doping concentration, the emission intensity of Ca13.88Al9.99Zn6O35: 0.12Dy(3+), 0.01Mn(4+) sample can be enhanced and the color tunability can be achieved. Ca14Al10Zn6O35: Dy3+, Mn4+, Na+ phosphors have potential application in solid-state lighting field.