<p>In this work, α-LiFe₅O₈ with a macro–mesoporous structure was synthesized using a multistep process. X-ray diffraction and Rietveld refinement confirm the formation of a single-phase, highly crystalline α-LiFe₅O₈ with an ordered cubic spinel structure (P4₃32), free of secondary phases after calcination. Scanning Electron Microscopy (SEM) reveals, an interconnected sponge-like mesoporous structure (~ 10&#xa0;nm), while electron paramagnetic resonance (EPR) confirms temperature-dependent Fe³⁺ super-exchange interactions in α-LiFe₅O₈. Over the studied temperature range α-LiFe₅O₈ exhibits semiconducting behavior. This semiconducting behavior is linked to the thermal activation of the small-polaron hopping transport process. Between 380 and 428&#xa0;K, the dc conductivity of α-LiFe₅O₈ becomes nearly temperature-independent, confirming the stability of conductivity with temperature. The electrical transport analysis reveals a temperature-dependent transition between distinct conduction mechanisms. At low temperatures, charge carriers follow Mott variable-range hopping (VRH), indicating strong localization within disordered states. In the intermediate region, the data fit the Shklovskii–Efros VRH, confirming the influence of Coulomb gap-controlled hopping. At higher temperatures, the transport is governed by the small-polaron hopping (SPH) mechanism, consistent with thermally activated carrier mobility. These results provide a coherent picture of the conduction behavior across the full investigated temperature range. For all measured temperatures, the conductivity spectra of α-LiFe₅O₈ are examined via universal power law, revealing a characteristic dispersive behavior. The material exhibits pronounced negative temperature coefficient behavior, characterized by two NTCR values (− 4.31% K⁻¹ at 343&#xa0;K and − 3.40% K⁻⁻¹ at 433&#xa0;K), highlighting the strong potential of α- LiFe₅O₈ for thermistor and temperature sensing applications.</p>