Clean　and　efficient　extraction　of　aluminum　hydroxide　from　coal　fly　ash　has　environmental　and　economic　benefits.　The　current　study　mainly　aimed　to　develop　an　efficient　and　nonhazardous　baking-electrolysis　process　to　extract　aluminum　hydroxide　from　coal　fly　ash.　During　acid　baking,　the　important　parameters　that　affect　aluminum,　iron,　and　calcium　leaching　efficiency　were　studied.　The　maximum　leaching　efficiency　of　aluminum　reached　86.8%　(iron　leaching　efficiency　was　61.0%　and　calcium　leaching　efficiency　was　83.0%)　under　the　optimal　conditions　of　T　=　200　degrees　C,　t　(acid　baking)　=　90　min,　and　t　(ball　milling)　=　5　min.　X-ray　diffraction,　scanning　electron　microscopy　and　laser　granulometry　were　used　to　investigate　the　mineralogy　phases,　microstructures,　particle　size　distributions,　and　the　mechanism　of　the　acid　baking　process.　X-ray　diffractometry　and　scanning　electron　microscopy　results　revealed　that　aluminum　hydroxide　with　porous　plate-like　structures　was　the　main　electrolytic　product.　The　electrolysis　mechanism　was　analyzed　by　cyclic　voltammetry.　This　method　offers　the　advantages　of　reusing　the　effluent　after　electrolysis,　and　the　hydrogen　product　is　a　clean　form　of　energy.　Thus,　the　proposed　baking-electrolysis　process　provides　a　promising　technique　as　an　efficient　and　potential　zero-waste　integrated　process　for　sustainable　valorization　of　coal　fly　ash.