Despite extensive research, structural and magnetic uncertainties of La2CrMnO6 double perovskites remain unresolved, requiring further investigation. This study examines the Fe substitution at the Cr site in La2Cr1-xFexMnO6 (x = 0.00, 0.50, 1.00) (LCFM), synthesized via the conventional solid-state reaction method. XRD and Rietveld refinement confirm the orthorhombic Pbnm phase in LCFM, with crystallite size and lattice parameters increasing with Fe substitution at the Cr site. FESEM analysis revealed a reduction in grain size while UV–Visible spectroscopy reveals a reduction in band gap. X-ray photoelectron spectroscopy (XPS) confirmed the presence of mixed oxidation states Cr3+/Cr6+, Fe2+/Fe3+, and Mn3+/Mn4+. Magnetic measurements of LCFM reveal increased Hc, decreased Mr, and preserved multi-domain structure upon Fe3+ substitution at the Cr3+ site, driven by superexchange and double exchange interactions. Reduced grain size, optical band gap, and magnetic properties in Fe-substituted La2CrMnO6 suggest its suitability for optoelectronic and spintronic applications.