Two-dimensional (2D) graphene oxide (GO) membranes (GOM) have great potential in separation applications. However, GOMs face two distinct challenges: low flux arising from their tight stacking and instability arising from re-exfoliation of GO sheets in solution. To address these challenges, herein, we report the functionalization of basal planes of GO layers with 2-[2-(3-Trimethoxysilylpropylamino)ethylamino]ethylamine (TSE), followed by transforming them into membranes through a two-step process. In the first step, the functionalized GO sheets were assembled onto the porous ceramic support. At this stage, the interlayer distance between GO sheets was modulated via TSE’s long hydrocarbon chain. Afterward, the free amines of TSE on functionalized GO membranes (fGOM) surface were cross-linked with trimesoyl chloride (TMC) to prepare a hydrophilic thin-layer on top of fGOM (TL-fGOM), further enhancing their stability. Further, TL-fGOMs were tested for oil-in-water-emulsion separation. The increased interlayer distance and the increased surface hydrophilic nature of TL-fGOM offered ultra-high water permeance, 4860 % higher compared to the non-functionalized GOM. Moreover, the separation efficiency of TL-fGOM improved from 37 % of that of ceramic membranes to 99.5 %. Additionally, they showed excellent anti-fouling properties. After exposing the membranes to 500 ppm emulsion for 10 hours in batches, the flux recovery ratio exceeded 90 %. The TL-fGOM in our work demonstrated outstanding performance in purifying oily emulsions containing diesel/toluene/heptane-in-water. All these results revealed that the appropriate functionalization of graphene oxide could assist in forming a thin layer of graphene oxide on the support membranes, offering high separation efficiency and fouling resistance. This approach can be extended further to utilize the graphene oxide membranes for practical applications.