Red phosphor is an important component of the phosphor-converted white light-emitting diodes (pc-WLEDs). The development of the novel red phosphor with excellent luminescence properties is of great significance for high performance WLEDs. In this study, NaGd0.4Eu0.6Mg1–xZnxWO6red phosphors with excellent luminescence properties were successfully synthesized and systematically investigated. Our results show that the Zn2+-doping concentration has significant effect on the microstructures and luminescence properties of the NaGd0.4Eu0.6Mg1–xZnxWO6phosphors. The NaGd0.4Eu0.6Mg1–xZnxWO6(0 ≤ x ≤ 0.7) samples are well crystallized pure solid solution sub-microcrystals, whereas the phase purity gradually decreases at 0.7