Abstract  The polycrystalline samples of Ba-modified Pb(Fe_1/2Nb_1/2)O₃ (i.e., (Pb_1-xBa_x)(Fe_1/2Nb_1/2)O₃ PBFN, with x=0,0.05,0.07) were synthesized by a mechanosynthesis (i.e., high-energy ball milling) route followed by a mixed oxide method. Structural analysis provides the information on formation of single-phase orthorhombic structure on substitution of a small amount (x=0.07) of Ba at the Pb-site of Pb(Fe_0.50Nb_0.50)O₃ (PFN). The ferroelectric–paraelectric phase transition in PFN was observed at 383 K, which decreases on increasing Ba-concentration in PBFN. Detailed studies of dielectric properties of PBFW show the following: (i) diffuse phase transition, (ii) low loss tangent, (iii) low activation energy, and (iv) low frequency dielectric dispersion. An anomaly in the ac conductivity was found very close to phase transition temperature. The activation energy is found to decrease from 0.19 to 0.01 eV on increasing Ba-concentration to 7% (x=0.07). Temperature field-dependent magnetization measurements of all the samples showed antiferromagnetic transition at ∼15 K (for x=0.07). PBFN sample showed a slight increase in the coercivity (i.e., from 400 Oe (PFN) to 500 Oe (PBFN, for x=0.07) at 2 K.