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.