In　this　work,　porous　PIL-TAs　were　reported　for　superhigh　capacity　and　reversible　NH3　uptake,　where　PIL-TAs　are　cobaltous　thiocyanate　(Co(II)(SCN)42-,　TA)　functionalized　poly　ionic　liquids　(PILs).　Due　to　the　structural　support　of　TA　as　well　as　the　interactions　between　TA　and　imidazolium　cation,　the　PIL-TAs　possess　porous　structure　and　optimized　properties.　Superhigh　NH3　uptake　capacity　of　13.2–20.1　mmol　g−1　at　STP　of　PIL-TAs　was　achieved,　which　is　higher　than　most　of　the　reported　sorbents.　In　detail,　the　cooperative　interactions　including　the　NH3　coordinating　with　Co(II)　instead　of　SCN-　and　hydrogen　bonding　of　C2H　in　imidazolium　(C2H…NH3)　benefit　to　high　capacity　of　NH3　uptake.　Reversely,　the　NH3　release　would　be　directed　by　the　competition　of　the　free　SCN-　with　NH3　to　reform　PIL-TAs.　The　competitive　interaction　with　SCN-　promotes　NH3　release　by　temperature　and　pressure　swinging,　which　contributes　the　adsorbents　recyclable.　The　cooperative　and　competitive　interactions　make　these　PIL-TAs　possess　high　gas　capacity　and　feasible　desorption,　which　might　be　a　potential　strategy　for　designing　novel　gas　sorbents.　©　2021　Elsevier　B.V.