<p>A comprehensive investigation of the semiconductor–metal–semiconductor-like transition (SMST) in LaFeO₃ nanoceramics, synthesized via a modified sol–gel auto-combustion method, was conducted at low temperatures. Scanning electron microscopy (SEM) of the fracture surface reveals a porous microstructure with an average grain size of approximately 60&#xa0;nm. X-ray photoelectron spectroscopy (XPS) confirms the presence of Fe²⁺, Fe³⁺, and Fe⁴⁺ ions and oxygen vacancies in the LaFeO₃ matrix. Impedance analysis indicates that the observed SMST behavior is associated with valence state transitions among Fe⁺³, Fe⁺², and Fe⁺⁴ ions. The Kohlrausch–Williams–Watts (KWW) parameter is less than unity, suggesting non-Debye-type relaxation, as supported by modulus spectroscopy. The temperature-dependent frequency exponent indicates that the conduction mechanism is governed by both correlated barrier hopping (CBH) and non-overlapping small polaron tunnelling (NSPT). A high dielectric constant in the low-frequency region confirms the dominant contribution of electrode polarization. Moreover, the temperature-dependent dielectric constant and tangent loss further validate the SMST behavior. This study uniquely demonstrates a semiconductor–metal–semiconductor-like transition (SMST) in LaFeO₃, unveiling an unconventional electronic response that has not been previously reported, thereby suggesting its potential as a promising material for phase-change memory and related technologies.</p>