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Barium mono-ferrite (BaFe2O4) and barium hexa-ferrite (BaFe12O19) nanoparticles were produced by the sol–gel auto-combustion method. The prepared nanoparticles were examined by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy (RAMAN), and Scanning electron microscopy (SEM) for structural, functional, and vibrational bonding, and morphological study, respectively. The optical, dielectric, and magnetic characteristics were explored by UV–visible spectroscopy, Fluorescence spectrophotometer, Impedance analyzer, and Vibrating sample magnetometer (VSM). The ferroelectric nature of magnetic nanoparticles was confirmed by the Multi-ferroic system. Electrochemical impedance spectroscopy monitored electrical properties by current–voltage (I–V) curves. The structure of BaFe2O4 was orthorhombic having space group Pnma 3 while BaFe12O19 was identified as hexagonal with space group P63/mmc (194). FTIR and Raman spectrum identified chemical structural bonds. SEM micrographs revealed the distinct size of nanoparticles. Saturation magnetization (Ms) for BaFe12O19 was 25.88 emu/g with a coercivity (Hc) value of 9668.05 and greater than BaFe2O4 with 1.4 emu/g and 2038. Di-electric properties of BaFe12O19 were higher than BaFe2O4 and not considered encouraging for photovoltaic applications. BaFe2O4 indicated balanced absorbance (1.03%) in the UV–visible region with 1.51 eV direct band gap that justified the main characteristics of a PV material. BaFe12O19 possessed high absorbance (37%) in the UV region with an indirect band gap of 1.24 eV that not believed as a viable choice for PV functioning. The fluorescence emission spectrum resulted higher concentration of 106 for BaFe12O19 while 51.3 for BaFe2O4 in the visible region. The highly concentrated materials could damage PV module by triggering hot spot. The I–V curves unveiled BaFe2O4 more respondents to dark and photo-current while BaFe12O19 possessed a negligible response. Above-stated results established that BaFe2O4 is comparatively a novel nano-ferrite that comprises more supportive properties for photovoltaic applications than BaFe12O19. [ABSTRACT FROM AUTHOR]