A　significant　amount　of　coal　fly　ash　is　generated　and　this　type　of　waste　material　causes　severe　environmental　hazards.　Metal　(Al　and　Fe)　extraction　from　coal　fly　ash　is　beneficial　to　the　resource　utilization　of　waste　coal　fly　ash.　However,　the　coexistence　of　Al　and　Fe　in　coal　fly　ash　means　that　the　separation　of　Al　and　Fe　is　required,　which　is　a　key　and　difficult　step　to　prepare　high　value-added　products　from　coal　fly　ash.　This　work　presents　a　novel　electrolysis　method　to　alter　the　charge　sequence　of　Al3+,　Fe3+,　and　H2O,　leading　to　a　process　different　from　their　natural　tendency　for　simultaneous　separation　of　Fe3+　and　Al3+,　and　extraction　of　Fe.　The　single　iron　removal　efficiency　was　43.48%,　and　the　aluminum　extraction　efficiency　was　＜0.30%　under　optimal　conditions.　The　iron　product　had　a　purity　of　98.3　wt%　Fe,　0.45　wt%　Al,　and　0.18　wt%　S.　This　process　occurs　without　chemical　additions　and　expensive　membranes,　avoiding　impurity　introduction,　slag　generation,　and　membrane　limitations.　Fe(s),　H-2(g),　Al-2(SO4)(3)(aq),　and　O-2(g)　are　the　main　products　during　the　electrolysis.　Flake　Fe　is　selectively　produced　instead　of　colloidal　Fe(OH)(3).　Fe　is　a　magnetic　substance　and　is　easier　to　remove　from　the　solution　by　magnets　than　colloidal　Fe(OH)(3).　H-2　is　a　green　fuel.　Wastewater　(Al-2(SO4)(3)(aq))　can　be　directly　used　to　further　extract　alumina.　Therefore,　this　study　provides　an　alternative　method　of　zero　pollution　discharge　for　simultaneous　separation　of　Fe3+　and　Al3+,　and　extraction　of　Fe　from　coal　fly　ash　leachate.