With the interest in using lead-free materials to replace lead-containing materials increasing, the use of Na 0.5 Bi 0.5 TiO 3 (NBT) has come into our sight. We studied the composition of NBT and found that NaBiTi 6 O 14 ceramics can be compositionally tuned by Mg-doping on the Ti-site to optimize the dielectric properties. In this study, Mg-doped NaBiTi 6 O 14 (NaBi(Ti 0.98 Mg 0.02 ) 6 O 14−δ ) ceramics were prepared by a conventional mixed oxide route at different sintering temperatures, and their dielectric properties have been studied at a wide temperature range. X-ray diffraction (XRD) patterns of the NBT-based ceramics indicate that all samples have a pure phase without any secondary impurity phase. The experimental data show that after Mg-doping, the relative permittivity and dielectric loss become lower at 1040, 1060, and 1080 • C except 1020 • C and at different frequencies from 10 kHz, 100 kHz to 1 MHz. Take 1060 • C for example, when the sintering temperature is 1060 • C at 1 MHz, the minimum relative permittivity of NaBiTi 6 O 14 is 32.9 and the minimum dielectric loss is 0.01417, the relative permittivity of NaBi(Ti 0.98 Mg 0.02 ) 6 O 14−δ under the same condition is 25.8 and the dielectric loss is 0.000104. We explored the mechanism of Mg-doping and surprisingly found that the dielectric property of NaBi(Ti 0.98 Mg 0.02 ) 6 O 14−δ becomes better owing to Mg-doping. Thus, NaBi(Ti 0.98 Mg 0.02 ) 6 O 14−δ can be used in microwave ceramics and applied to new energy materials.