A novel tantalate red-emitting phosphors NaCa1-xEuxTiTaO6 (x = 0.02-0.50) is synthesized via the traditional solid-state reaction sintering. The photoluminescence properties, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal stability are characterized in detail. Photoluminescence spectra show strong red emission monitored at 614 nm at lambda(ex) = 395 nm. The spectral properties exhibit excellent color purity and chromaticity coordinate (CIE) characteristics. White light-emitting diodes (w-LEDs) device are fabricated by the prepared phosphors and show high quality of color-rendering index. The investigated results suggest that the Eu3+-doped NaCaTiTaO6 phosphors can be as potential substitute red phosphors for w-LEDs.