Rhenium　is　a　key　metal　in　high　technology.　It　is　important　how　to　effectively　and　selectively　recover　perrhenate　from　copper　smelting　acidic　effluent.　A　CH3COOK　activated　hierarchical　biochar　from　bamboo　shoot　shell　was　prepared　to　efficiently　and　selectively　adsorb　perrhenate　in　the　acidic　solution.　Some　adsorption　experiment　factors　such　as　initial　pH,　adsorbent　dose,　contact　time,　and　temperature　have　been　comprehensively　tested.　The　maximum　adsorption　capacity　of　the　adsorbent　for　perrhenate　reached　up　to　84.63　mg/g.　Spontaneous　physical　adsorption　was　possible　adsorption　mechanism　according　to　thermodynamic　analysis.　The　intensified　hydrophobic　surface　and　graphitic　defect　structure　of　the　adsorbent　accounted　for　its　excellent　selectivity　to　hydrophobic　perrhenate.　Regeneration　experiments　showed　that　the　CH3COOK　activated　hierarchical　biochar　was　reusable.　The　CH3COOK　activated　hierarchical　biochar　has　the　high　potency　for　highly　efficient　and　selective　recovery　of　perrhenate　from　the　acidic　solution　generated　by　the　copper　smelting　process.