This work presents a simple and fast seed-mediated synthesis of ZnO@γ-Fe2O3 nanospheres with structural and optical characterization. A sequential growth of ZnFe2O4 and γ-Fe2O3 components on preformed ZnO seeds was achieved by a sol–gel route. The High-Resolution Transmission Electron Microscopy (HRTEM) disclosed the morphology, particle size and confirmed the core-shell structure of the nanospheres. Qualitative X-ray Photoelectron Spectroscopy (XPS) asserted the presence of O2–, Zn2+ and Fe3+ ions. The complementarity of X-ray Diffraction (XRD) and X-ray Absorption Near Edge Structure (XANES) studies were used for the structural characterization and building up the core-shell model. The UV–Vis and Photoluminescence (PL) spectroscopies were used for optical characterization. The consistency of the bandgap (Eg) values obtained with both techniques assures the obtained results.