<p>Al–Cr and Al–Cr–Ni alloys were synthesized <i>via</i> <i>in-situ</i> aluminothermic reduction of CrO₃ and NiO in molten aluminum at 1000&#xa0;°C using cryolite as a flux. XRD and SEM/EDX analyses confirmed the formation of Al–Cr intermetallics (Al₇Cr, Al₄Cr, Al₈Cr₅) in the binary alloys, while the ternary alloys additionally contained (Al₃Ni) and complex Al–Cr–Ni phases (AlCrNi₂, Al_0.983Cr_0.017, and Cr₇Ni₃). Differential thermal analysis (DTA) revealed sequential events corresponding to CrO₃ decomposition, aluminum melting, and rapid aluminothermic reduction accompanied by intermetallic formation. Chromium recovery increased steadily with CrO₃ content in the absence of NiO but was markedly reduced in its presence due to competitive reduction. Nickel recovery in the Al–Cr–Ni alloys was relatively consistent, ranging from 0.83 to 0.99 wt pct Ni, corresponding to 30 to 33 pct of the added NiO. Although NiO reduction is thermodynamically more favorable than Cr₂O₃ reduction, actual recoveries were influenced by kinetic factors including mixing efficiency, temperature, fluxing, and slag entrapment. Cryolite fluxing and mechanical stirring were identified as critical parameters governing both the rate and extent of metal recovery.</p> Graphical Abstract <p></p>