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　SCNwith　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.