Nanocrystalline Fe3O4 and α-Fe2O3 particles were successfully synthesized by hybrid electrochemical-thermal method. The as-prepared compound was calcined for an hour at different temperature. The crystallite size, morphology, and chemical state of the synthesized powders were characterized by powder XRD, TG-DTA, XPS, SEM/EDAX, TEM, FT-IR, and UV–Vis spectral techniques. Rietveld refinement of X-ray data of the calcined compound exhibits rhombohedral (hematite) structure with space group of R3c (No. 167). The thermal behavior of as-prepared compound was examined. Scanning electron photomicrographs show uniform, randomly oriented hexagonal and spherical like morphology and EDAX measurement showed its chemical composition. The TEM result revealed that the particle morphology was hexagonal with spherical in nature and sizes were in the order of 40–60 nm in diameter and 120–200 nm in length. The absorption and blue shift were noticed in UV–Vis absorption spectra and the band gaps were found to be 4.22–4.29 eV. The electrochemically generated Fe3O4 and α-Fe2O3 nanoparticles were used to fabricate ZnCoαFe2O3 composite thin films and its corrosion behavior was analyzed by anodic polarization, Tafel extrapolation, and electrochemical impedance spectroscopy (EIS). The results indicate that the ZnCoαFe2O3 composite thin films have potential applications to corrosion protection.