The Bi1 − xBaxFeO3 (BiBaFeO3) multiferroic nanoparticles with different Ba molar concentrations were fabricated in reliance on the solid-state reaction technique. Nanostructures of the prepared samples were confirmed by X-ray diffraction (XRD) together with Fourier transforms infrared (FTIR) spectroscopy, whereas the ac conductivity, dielectric and ferroelectric features were examined depending on the RLC Bridge, and Sawyer–Tower circuit. XRD patterns displayed the creation of rhombohedral–hexagonal single-phase of BiBaFeO3. The formation of BiBaFeO3 multiferroic nanoparticles was confirmed by FTIR spectra. Curie temperature (TC) was observed around 1121–1189 K. Ferroelectric polarization was enhanced with remnant polarization of 88.8 µC/cm2 by Ba2+ ions substitution at x = 0.15 mol%. Besides, ac electrical conductivities as a function of frequency as well as temperature were reported for all BiBaFeO3 multiferroic nanoparticles, which exhibit a strong frequency dependence with conduction mechanism is the correlated barrier hopping (CBH) model. The obtained high polarization and Curie temperature enhance their use in information storage devices.