In this paper, a series of Eu3+-activated double-pemvskite Ca2LaTaO6 (abbreviated as CLT:xEu(3+); x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) red-emitting phosphors have been successfully synthesized via the conventional high-temperature solid-state reaction method. These samples were characterized by X-ray diffraction, Rietveld refinement, field-emission scanning electron microscope, elemental mapping, energy-dispersive spectrum, room-temperature photoluminescence, decay lifetimes, quantum efficiency, CIE color coordinates, and temperature-dependent emission spectra. Interestingly, under blue excitation into the F-7(0)-> D-5(2) transition of Eu3+ at 466 nm, the CLT:xEu(3+) phosphors could emit bright red light corresponding to the D-5(0)-> F-7(J) (J = 1, 2, 3, 4) transitions. Their luminescence properties have been investigated as a function of the Eu3+ ions concentration. It was found that the CLT:0.4Eu(3+) sample exhibited the strongest emission intensity, and the concentration quenching effect was caused by the dipole-dipole interaction among Eu3+ activators. Impressively, the emission intensity of the as-prepared CLT:0.4Eu(3+) phosphors was about 4.3 times higher than the commercial Y2O3:Eu3+ red phosphors. Moreover, the CLT:0.4Eu(3+) sample had excellent CIE color coordinates of (0.665, 0.334) and supereminent color purity of 95.3%. Notably, the study on temperature-dependent emission spectra of the CLT:0.4Eu(3+) sample revealed its good thermal stability and color stability at high temperatures. These excellent photoluminescence properties of CLT:0.4Eu(3+) phosphors indicated their promising application potential in white light-emitting diodes as blue-light-excitable red phosphors.