Abstract K0.5Na0.5NbO3 (KNN):xEu3+ materials were fabricated via the conventional solid-state reaction method. The microstructure and photoluminescence property of KNN:xEu3+ were investigated. XRD and SEM analyses evidenced that the fergusonite-type structure EuNbO4 were homogeneously precipitated among KNN host. Photoluminescent properties of KNN:xEu3+ were significantly influenced by the variations between KNN and EuNbO4 phase. Within the quenching concentrations, the KNN:xEu3+ exhibited intense narrow band red emissions centered at 615 nm from 5D0 → 7F2 transition with good thermal stability (20–200 °C), under the excitation wavelength at a near-ultraviolet (393 nm) or blue light (464 nm). The red emission intensity reached a maximum at x = 0.20 due to the concentration quenching effect. Nevertheless further increasing the Eu3+-doped concentration over x = 0.25 did not decrease the red emission intensity, but significantly enhanced the red emission due to the intrinsic luminescence of EuNbO4. These results suggest the KNN:xEu3+ could be potentially applicable in W-LEDs under near-ultraviolet or blue chip excitation.