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Bi1−xBaxFeO3 (x = 0, 0.1, 0.2 and 0.3) ceramic nanopowders were prepared by the ethylene glycol-based sol-gel method followed by heat treatment at 800 °C for 1 h. The effect of Ba2+ ions substitution on the structural and magnetic properties of the BiFeO3 (BFO) has been investigated. X-ray diffraction along with Rietveld refinement of Ba-substituted samples showed the presence of both rhombohedral (R3c) and pseudocubic (Pm3m) phases. Microstructural analysis confirmed the formation of homogeneous and nearly cubic nanoparticles. Result shows a reasonable enhancement in saturation magnetization of the substituted samples. Bi0.9Ba0.1FeO3 having 30% R3c and 70% Pm3m phases, show maximum saturation magnetization, i.e., 0.32 emu/g at room temperature. The magnetic properties of synthesized ceramics have been discussed in terms of FeO6 octahedra tilting with respect to body diagonal <111> of the pseudocubic system. By combining magnetic measurements with thermal analysis, it is shown that the substitution of Ba for Bi site causes an enhancement in magnetic transition temperature (TN). [ABSTRACT FROM AUTHOR]