A series of Eu3+ doped and Li+, Eu3+ co-doped Gd2ZnTiO6 (GZT) red-emitting phosphors were successfully prepared by sol-gel method. The effects of Li+ and Eu3+ ions doping on the crystal structure, microstructure and luminescent properties of the samples were studied. Results show that the obtained double perovskite Gd2ZnTiO 6∶Li+,Eu3+(GZT∶Li+,Eu3+) phosphors crystallized in the monoclinic space group P21/n and are composed of irregular particles with the size of 10 μm. Under the excitation of 395 nm near ultraviolet light, the emission spectrum of GZT∶Eu3+ shows a typical linear characteristic spectrum of Eu3+ ions. The center position of the emission peak is located at 615 nm, which belongs to the 5D0→7F2 transition of Eu3+. The optimum doping concentration of Eu3+ is 0.07 (mole fraction). The obtained samples show obvious concentration quenching effect, and its mechanism can be identified as the electric dipole-dipole interactions(d-d). In addition, it is also found that Li+ doping has no effect on the crystal structure and micro morphology of the samples, but a certain amount of Li+ doping can significantly enhance the fluorescence intensity of the samples. When the concentration of Li+ is 0.05, the intensity of the main emission peak of the phosphor is the largest, which is 4.3 times of the original, indicating that high brightness GZT red-emitting phosphor can be obtained by co-doping Li+ and Eu3+. The CIE color coordinates of GZT∶0.14Eu3+,0.05Li+ phosphor is located at (0.631 1,0.375 3) close to the standard red color coordinates (0.670, 0.330), which is a potential red-emitting phosphor for LED.