Organic　templates　play　a　crucial　role　in　zeolite　synthesis,　but　their　use　causes　serious　pollutant　emissions　and　increases　product　costs.　Herein,　we　report　a　template-free　approach　to　synthesize　both　microporous　and　hierarchical　ZSM-5　zeolites　from　natural　aluminosilicate　mineral,　which　is　achieved　by　(1)　utilizing　the　mother　liquid　to　construct　mesopores　without　using　any　mesoscale　template　and　(2)　reusing　the　Si-rich　alkali　liquor　and　ion-exchanging　solution　to　improve　the　atom　economy　without　any　alkali/acid　liquor　discharges.　The　results　show　that　the　resultant　zeolites　own　more　open　pore　channels　and　less　strong　acid　sites　compared　with　a　conventional　ZSM-5　zeolite　and　demonstrate　superior　catalytic　activity　in　n-octene　hydroisomerization.　Significantly,　compared　with　the　traditional　synthesis　process,　our　approach　can　greatly　reduce　the　material　and　energy　consumptions　and　pollutant　discharges　while　significantly　increase　the　raw　material　utilization　efficiency,　endowing　itself　as　an　economic,　eco-sustainable,　and　industrially　feasible　process.　©　2017　American　Chemical　Society.