Polycrystalline Bi0.90Eu0.10Fe1-xVxO3 (BEFVO) (where x = 0.00 to 0.10) ceramics were synthesized by the solid-state reaction method. The X-ray diffraction (XRD) pattern revealed that all the samples possess hexagonal crystal structures with some impurity peaks. Gold Schmidt’s tolerance factor of the samples was found 0.8436 to 0.8478 which represents more stability of the doped BiFeO3 (BFO) than parent BFO. The crystallite size was found in the range of 65–33 nm. The density gradually increases with increasing the V concentration and the maximum bulk density (ρB = 6.981 g/cm3) is obtained for the x = 0.10 sample. The obtained average grain size is found in the micrometer range and the values are in the range of 1.31–0.74 µm. The maximum dielectric constant of 2577 at 102 Hz is found for the x = 0.07 sample. The resistivity decreases with doping concentration as a result of ac conductivity increases. The highest transition frequency of long-range to short-range mobility of charge carriers is obtained for the x = 0.07 sample. The highest real part of the initial permeability of 25.24 is found for x = 0.07 multiferroic ceramics. For the x = 0.07 sample, the maximal saturation magnetization is found to be 1.91 emu/g. The studied samples comprise large electric polarization and the optimum polarization of 7.5 μc/cm2 is observed for the x = 0.07 composition.