Selective　adsorption　towards　heavy　metals　from　the　industrial　wastewater　is　of　great　value.　Here,　we　developed　a　green　synthetic　strategy　to　acquire　a　polythiophene　(PTh)/MnO2　composite　in　the　aqueous　medium.　The　produced　core-shell　composite,　which　featured　abundant　sulfurs　and　hydroxyls,　provided　a　platform　for　the　effective　heavy　metal　ion　capture,　resulting　in　a　rapid　adsorption　equilibrium　within　30　min,　and　in　novel　adsorption　capacities　of　82.10,　30.72　and　60.79　mg　g−1　for　Pb2+,　Zn2+　and　Cu2+,　respectively.　It　also　showed　developable　selectivity　towards　these　heavy　metal　ions,　which　could　be　tuned　by　the　core　MnO2,　with　a　competition　factor　order　of　P(1.22,　Pb2+)∼P(1.02,　Zn2+)P(0.508,　Cu2+).　We　showed　that,　through　experiments,　characterizations　and　DFT　calculation,　this　selectivity　resulted　from　its　synergetic　self-doping　nature　between　PTh　and　MnO2,　by　which　the　PTh　would　protect　hydroxyls　from　being　associated　with　H+　before　adsorption,　enabling　hydroxyls　catch　heavy　metals　in　a　much　efficient　and　selective　manner.　Moreover,　this　self-doping　nature　allowed　our　composite　to　be　robustly　recycled　for　more　than　five　cycles　through　a　simply　acid-base　treatment.　The　provided　design　principle　for　the　task-specific　adsorbent　herein　would　contribute　to　address　challenges　concerning　heavy　metal　selective　capture　in　the　environmental　field.　©　2022　Elsevier　Ltd