To produce over 99.9% of high-purity Al from Al–Fe alloy containing Al6Fe and Al–Fe–Si alloy containing β-AlFeSi by electrorefining, their anodic dissolution and cathodic electrodeposition characteristics were investigated in an EmImCl–AlCl3 ionic liquid electrolyte at 323 K. Constant potential electrolysis showed that Fe dissolved from Al–Fe anode at 0.7 V vs Al/Al(III) and from Al–Fe–Si anode at 1.4 V, and was co-deposited with Al on the cathode. Notably, anodic dissolution potential of Fe was changed by forming β-AlFeSi, and Si did not dissolve from β-AlFeSi at either potential. A combination of controlled anodic dissolution potential and the use of the Al alloy containing β-AlFeSi further suppressed the dissolution and cathodic co-deposition of Fe, affording high-purity Al on the cathode.