In this study, the synthesized samples La0.5Sm0.2Sr0.3Mn1-xFexO3 (x = 0.05, 0.15 and 0.20) were thoroughly investigated for their crystalline structure, electrical conductivity, and dielectric properties, the samples were prepared using autocombustion method. According to the X-ray diffraction study, the samples crystallized in an orthorhombic symmetry with the Pnma space group. To measure the dielectric characteristics, impedance spectroscopy was conducted over the temperature range of 100–260 K and a frequency range of 100 Hz to 1 MHz. Measurements of AC conductivity are indeed utilized to investigate the transport properties of materials being studied. The results indicated that both temperature and frequency significantly influence the conduction process. Three theoretical hypotheses were proposed to explain the hopping conduction: overlapping large polaron tunneling (OLPT), the non-overlapping small polaron tunneling (NSPT) mechanism, and correlated barrier hopping (CBH). It is also shown that the conductivity diminishes with an increase in Fe content. La0.5Sm0.2Sr0.3Mn1-xFexO3 (x = 0.05, 0.15 and 0.20) can be used in electronic applications because of the high permittivity values confirmed by the dielectric measurements. With the aim of evaluating the distinct impacts of electrodes, grain boundaries, and grains on the complex impedance results, an appropriate alternative electrical circuit was utilized. Analysis of the sample's modulus indicated non-Debye characteristics and electrical relaxation phenomena. The materials exhibit good electrical properties, as well as strong chemical and thermal stability.