The　synthesis　of　1-methoxy-2-propanol　(1-MP),　which　is　expected　as　a　safe　alternative　for　toxic　ethylene　glycol　ether,　is　highly　demanded　in　chemical　engineering.　Herein,　we　report　a　series　of　task-specific　anion-functionalized　poly(ionic　liquid)s　(PILs)　to　trigger　an　effective　catalysis　in　the　1-MP　production　through　a　reaction　of　propylene　oxide　(PO)　and　methanol.　The　acquired　PIL　catalysts,　which　are　induced　by　phenolate　anions,　allow　extraordinary　PO　conversion　of　90.8　%　and　outstanding　1-MP　yield　and　selectivity　of　86.5　%　and　95.3　%　under　very　mild　conditions.　It　also　feasibly　applies　to　the　catalysis　of　a　wide　range　of　alcohols　and　PO　to　synthesize　propylene　glycol　ethers　(PGEs),　and　shows　robust　and　facilitate　reusability.　Through　a　DFT　calculation　and　in-situ　2D-IR　survey,　we　reason　that　these　significant　performances　are　enabled　by　hydrogen-bonding　interaction　from　the　imidazole　on　the　backbone　for　PO　activation,　and　by　the　unique　nucleophilicity　of　anions　for　the　generation　of　activated　methanol.　©　2023　Elsevier　B.V.