We investigate the impact of Ni insertion on the structural, optical, and magnetic properties of Ba0.8La0.2Fe12–x
Ni
x
O19 hexaferrites (Ni substituted La-BaM hexaferrites). Samples were prepared using the conventional co-precipitation method and sintered at 1000 °C for 4 hours to assist the crystallization process. An analysis of the structure of the samples was carried out using an x-ray diffraction (XRD) spectrometer. The M-type hexagonal structure of all the samples was confirmed using XRD spectra. The lattice parameters a and c were found to be in the ranges of 5.8925±0.001 nm–5.8952±0.001 nm and 23.2123±0.001 nm–23.2219±0.001 nm, respectively. The M-type hexagonal nature of the prepared samples was also indicated by the presence of corresponding FT-IR bands and Raman modes in the FT-IR and Raman spectra, respectively. EDX results confirmed the successful synthesis of the samples according to the required stoichiometric ratio. A UV-vis spectrometer was used to record the absorption spectra of the prepared samples in the wavelength range of 200 nm–1100 nm. The optical energy bandgap of the samples was found to be in the range of 1.21 eV–3.39 eV. The M–H loops of the samples were measured at room temperature at an applied magnetic field range of 0 kOe–60 kOe. A high saturation magnetization of 99.92 emu/g was recorded in the sample with x = 0 at a microwave operating frequency of 22.2 GHz. This high value of saturation magnetization is due to the substitution of La3+ ions at the spin-up (12k, 2a, and 2b) sites. The Ni substitution is proven to be a potential candidate for the tuning of the optical and magnetic parameters of M-type hexaferrites. Therefore, we suggest that the prepared samples are suitable for use in magneto-optic applications.