Separating　anionic　surfactant-stabilized　oil-in-water　emulsions　remains　a　critical　challenge　due　to　the　presence　of　surfactants.　In　this　study,　we　developed　a　unique　collagen　fiber-based　CFM-PEI-TiO2　with　superhydrophilic　and　underwater　superoleophobic　properties,　enabling　efficient　separation　of　various　anionic　surfactant-stabilized　oil-in-water　microemulsions　and　nanoemulsions　through　charge　demulsification　effects.　The　membrane　achieved　high　separation　flux　(1458.50　L·m−2·h−1)　and　separation　efficiency　(99.94%)　simultaneously.　Importantly,　the　membrane　exhibited　remarkable　mechanical　durability,　as　it　remained　capable　of　separating　diverse　oil-in-water　emulsions　even　after　being　subjected　to　abrasion　with　sandpaper　for　500　cycles,　highlighting　its　long-term　durability　and　economic　viability.　The　robust　membrane　also　demonstrated　excellent　recyclability,　with　a　separation　efficiency　of　over　99%　after　twelve　cycles　and　a　flux　of　1299.10　L·m−2·h−1　after　fifteen　cycles.　These　properties　can　be　attributed　to　the　PEI-induced　electrostatic　interactions　and　the　enhanced　superhydrophilic-superoleophobic　interaction　provided　by　TiO2　on　the　unique　collagen　fiber　membrane.　The　outcomes　emphasize　the　versatility　and　potential　of　our　membrane　in　overcoming　the　challenges　associated　with　emulsified　oily　wastewater.　©　2024　The　Institution　of　Chemical　Engineers