2D graphene oxide (GO) membranes are gaining prominence for water reclamation from oily wastewater. Unresolved challenges include low membrane permeance from tight sheets and fouling during separation. In this work, a bioinspired Arabic gum (AG) was used as an intercalated agent with the help of glutaraldehyde to improve the GO membranes’ permeation and fouling resistance. The 2D-laminated separating layer is crafted through a self-assembling innovative approach utilizing pressurized dead-end assembly. The Arabic gum intercalated graphene oxide-modified ceramic membrane (AGIGO-CM) appeared superhydrophilic and underwater (UW) superoleophobic with a UW oil contact angle (UWOCA) of 156.1 ± 1.2°. The membrane prepared with 1 mg of AGIGO (AGIGO-1-CM) offers a flux of 17 times higher than pristine graphene oxide (p-GO) while maintaining a separation efficiency of >99% during the separation of the oil-in-water emulsions. Molecular dynamics (MD) simulations showed AG intercalation expanding the interlayer distance by up to 20 Å, with AGIGO having a higher fractional free volume (FFV) of 0.986 compared to p-GO’s 0.599. AGIGO-CM displayed lower interfacial formation energy (EIFE) of −1865.2 kcal/mol versus −765.5 kcal/mol for p-GO, indicating easier separation. It is further supported by the substantial interfacial thickness of 148 Å for AGIGO-CM compared to 53.0 Å for the p-GO membranes. AGIGO-CM showed minimal fouling, retaining >99% separation efficiency for 6 h. Compared to p-GO-CM, AGIGO-CM flux decreased by only 17.84% versus 44.72%. AGIGO-CM exhibited stability even in acidic and basic environments, showcasing its potential for high performance.