The new red-emitting phosphors of Eu3+-doped triple orthovanadates NaALa(VO4)2 (A = Ca, Sr, Ba) were prepared by the high-temperature solid-state reaction. The formation of single phase compound with isostructural structure of Ba3(VO4)2 was verified through X-ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition 5D0→7F2 of Eu3+ ions. Their potential applications as red-emitting phosphors for solid-state lighting were evaluated in comparison with the Eu3+-doped lanthanum orthovanadate LaVO4 and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red-emitting phosphor for the application on white LEDs under irradiation of near-UV or blue chips.