In this work, a Mn-and Yb-doped BaTiO3-(Na0.5Bi0.5)TiO3 ferroelectric relaxor was designed and prepared. The effects of Mn on the microstructures, dielectric and electrical properties of the ceramics were investigated. The X-ray structural analysis shows a perovskite structure. The SEM images show the homogeneous microstructure of ceramics with an average grain size of about 1 μm. The temperature-dependent permittivity shows relaxor characteristics as Mn-doped. Mn at a low level (x ≤ 0.005) is beneficial for low dielectric loss and high resistivity. The maximum resistivity of ≥3 × 1012 Ω cm and minimum dielectric loss of ≤0.06 can be achieved at x ≤ 0.005. The resistivity of the ceramics follows the Arrhenius law with activation energy decreasing from ~1.31 to 1.01 eV as x increases. With lower Mn dopant, oxygen vacancies and charge carrier concentration partially decrease with Mn doping, which is helpful to improve the insulation resistance and decrease the dielectric loss.