Oil/water　separation　of　emulsion　stands　as　one　of　the　most　arduous　and　challenging　aspects　in　oily　wastewater　treatment　which　represents　a　perennial　trouble　for　humanity.　Herein,　positively　charged　hydrophobic　polymer　foams　(PCHPFs)　were　fabricated　by　water-in-oil　(W/O)　high　internal　phase　emulsion　(HIPE)　polymerization　followed　by　quaternization,　employing　4-vinylbenzyl　chloride　(VBC)　and　4-tert-butylstyrene　(tBS)　as　the　comonomers.　The　quaternization　degree　of　PCHPFs　which　can　be　adjusted　by　varying　the　VBC/tBS　ratio　has　an　important　influence　on　the　emulsion　separation　performance　based　on　the　charge　demulsification　mechanism.　The　porous　morphologies　of　PCHPFs　were　revealed　by　SEM.　The　successful　fabrication　of　PCHPFs　was　confirmed　by　FTIR　and　XPS.　As　VBC/tBS　ratio　increased　from　0.5:1–5:1,　the　emulsion　separation　efficiency　of　PCHPFs　first　increased　to　a　maximum　of　95.9　%　at　2:1　and　then　decreased.　Additionally,　the　PCHPFs　demonstrated　robust　hydrophobicity　(water　contact　angles　＞　143°),　exceptional　oil-water　selectivity,　remarkable　oil-water　separation　capability,　coupled　with　a　certain　absorption　capacity　for　various　oils　and　organic　solvents　(5–14　g/g).　Given　these　advantages,　PCHPFs　are　anticipated　to　emerge　as　an　ideal　solution　for　emulsion　separation.　Most　importantly,　the　methodology　for　generating　PCHPFs　via　quaternization　in　this　research　offers　an　innovative　avenue　in　the　design　of　charge　demulsification　materials.　©　2025