A common method for reducing waste and environmental problems brought on by landfills is to reuse waste, especially heavy metals such as iron. Automotive industrial waste containing Fe-rich metal is successfully transformed into a highly pure structure of Fe2O3 using an etching method with HNO3 acid. This resulting structure serves as a precursor for synthesizing LaNi1-xFexO3±δ perovskite conducting materials. The desired perovskite conductive phase can be produced by substituting Fe2O3-treated waste at the B-site (Ni position) before calcination at 1200 °C. However, LaNiO3±δ and LaNi0.6Fe0.4O3±δ could not be synthesized under ideal conditions, as indicated by XRD analysis using TOPAS software, which revealed the presence of undesirable phases. Both compounds, LaNiO3±δ and LaNi0.6Fe0.4O3±δ demonstrated electrical conductivity with values of 362 S/cm and 42 S/cm at 550 °C, respectively. Nonetheless, electrical conductivity of both compounds decreased due to unintended phase contamination during the synthesis process. The Fe2O3-substituted compounds at the Ni position, in an exact amount of 1 mol, exhibited minimal electrical conductivity. Although the synthesis conditions to produce a single phase of LaFeO3±δ were identified, LaFeO3±δ, despite its low electrical conductivity, is frequently used in electrical devices as a gas detection sensor. The thermal expansion coefficient of all synthesized waste samples is represented in the range of 12–13 × 10−6 °C−1, which is comparable to IT-SOFC electrolyte materials. Furthermore, microstructural investigation revealed that the introduction of Fe into LaNiO3±δ reduced particle size and porosity, ultimately resulting in higher densities. These findings were confirmed through synchrotron radiation x-ray tomographic microscopy (SR-XTM) analysis. The research suggests that converting Fe-waste into a pure phase of Fe2O3 using a strong acid etching technique can serve as a viable precursor for synthesizing conductive materials. This approach enhances the value of industrial waste while also reducing its volume.