► Immobilization of Zr-rich radioactive metallic wastes via alloy melting route. ► First detail report on metallurgical characterizations of Fe–Cr–Ni–Zr alloys. ► Identification of suitable base alloy composition. Alloy melting route is currently being considered for radioactive hulls immobilization. Towards this, wide range of alloys, belonging to Zirconium–Iron binary and Zirconium–Stainless steel pseudo-binary systems have been prepared through vacuum arc melting route. Detail microstructural characterization and quantitative phase analyses of these alloys along with interaction study between Zirconium and Stainless steel coupons at elevated temperatures identify Zr(Fe,Cr) 2, Zr(Fe,Cr), Zr 2(Fe,Cr), Zr 3(Fe,Ni), Zr 3(Fe,Cr), Zr 3(Fe,Cr,Ni), β-Zr and α-Zr as the most commonly occurring phases within the system for Zirconium rich bulk compositions. Nano-indentation studies found Zr(Fe,Cr) 2 and Zr(Fe,Cr) as extremely hard, Zr 3(Fe,Ni) as moderately ductile and β-Zr, Zr 2(Fe,Cr) as most ductile ones among the phases present. Steam oxidation studies of the alloys, based on weight gain/loss procedure and microstructural characterization of the mixed oxide layers, suggest that each of the alloys responded to the corrosive environment differently. Fe 2O 3, NiFe 2O 4, NiO, monoclinic ZrO 2 and tetragonal ZrO 2 are found to be most common constituents of the oxide layers developed on the alloys. Integrating the microstructural, mechanical and corrosion properties, ZrFeCrNi3 (Zr: 84.00, Fe: 11.20, Cr: 3.20, Ni: 1.60, in wt.%) is identified as the acceptable base alloy for disposal of radioactive hulls.