A new, highly efficient deep red-emitting phosphor Ca14Al10Zn6O35:Mn(4+) was developed as a component of solid-state white light-emitting diodes (LEDs). The structural and optical characterization of the phosphor is described. The phosphor exhibits strong emission in the range of 650-700 nm when excited by 460 nm excitation, with a quantum efficiency approaching 50%. Concentration dependence of Mn(4+) luminescence in Ca14Al10Zn6O35:Mn(4+) is investigated. Attempts to understand the thermal stability on the basis of the thermal quenching characteristics of Ca14Al10Zn6O35:Mn(4+) is presented. The results suggest that phosphors deriving from Ca14Al10Zn6O35:Mn(4+) have potential application for white LEDs. In addition, influence of cation substitution on the luminescence intensity of these phosphors is elucidated.