In the current study, we report a comprehensive evaluation of the microstructures, optical, dielectric and magnetic traits of Ti-substituted perovskite structured lanthanum ferrite with chemical compositions LaTixFe1−xO3 (x = 0, 0.05, 0.15, 0.25). X-ray diffraction with Rietveld refinement and Raman analysis confirmed that both pure and Ti-substituted LaFeO3 maintained single-phase orthorhombic phase with Pbnm symmetry. Fourier transform infrared spectroscopy (FTIR) studies revealed the information about the positions of the ions and their bonds within the lattice structure of the LaFeO3. The spherical shaped morphology of all products was confirmed by SEM. The quantitative chemical composition and their distribution were confirmed by EDAX and mapping. The UV-Vis spectroscopic studies showed an excitonic absorption edge at 590 nm is ascribed to the electronic transition from O2p→Fe3d. Optical band gap (Eg) values were assessed by applying Tauc schemes, showed that Eg values are in a narrow range (1.85–2.02 eV). The dielectric properties such as, dielectric constant (ε’), dielectric loss (tan δ) was examined by varying with temperature and frequency. The magnetic results revealed weak ferromagnetic nature trait at 300 K. The variation in Ms (saturation magnetization), Hc (coercivity) and Mr (remanence) values were observed with increasing Ti substitution level.