Cationic　surfactant-stabilized　oil-in-water　emulsions　pose　a　significant　challenge　in　separation　due　to　the　presence　of　surfactants.　Herein,　we　develop　a　collagen-fiber-based　CFM-PMDA-TiO2　membrane　with　unique　infiltration　properties　capable　of　efficiently　separating　cationic　surfactant-stabilized　oil-in-water　emulsions　by　exploiting　the　charge-demulsification　effect.　The　membrane　exhibits　superhydrophilic　and　submerged　superoleophobic　properties,　making　it　highly　suitable　for　separating　a　wide　range　of　commercially　available　cationic　surfactant-stabilized　oil-in-water　microemulsions　and　nanoemulsions,　which　demonstrates　an　exceptional　separation　efficiency　as　high　as　99.86%　and　an　impressive　flux　of　up　to　1436.40　L　m-2　h-1.　Furthermore,　even　after　a　strong　subjecting　of　the　membrane　to　sandpaper　abrasion　and　a　full　15　time　use,　the　separation　efficacy　of　oil-in-water　emulsions　is　retained,　highlighting　the　durability,　reusability,　and　economic　viability.　We　propose　that　these　features　are　enabled　by　the　electrostatic　interactions　triggered　from　pyromellitic　dianhydride　(PMDA)　and　superhydrophilic-superoleophobic　membrane　intensified　by　the　TiO2　on　the　unique　collagen　fiber　membrane.　Outcomes　emphasize　the　versatility　and　potential　of　our　membrane　in　addressing　emulsified　oily　wastewater　hurdles.　©　2023　American　Chemical　Society