The rapid development of the petrochemical industry and associated wastewater, has led to an increasing demand for membrane technologies with enhanced permeability and anti-fouling properties in order to treat the wastewater effectively. The sustainable development of appropriate high-performance membranes requires continuous interaction between engineering practice and research. Herein, based on the laminar and fouling-resistant properties of graphene oxide (GO), and employing a layer-by-layer (LBL) assembly method with stable EDA cross-linking, a new modified graphene oxide/polyvinylidene difluoride (GO/PVDF) laminar membrane was fabricated. The membrane, with a layer spacing of approximately 0.94 nm, was applied for the first time to improve the removal of low molecular weight aromatic compounds from petrochemical wastewater. The results showed that the membrane exhibits outstanding long-term stability for treating real petrochemical wastewater, with the permeate COD maintained below 50 mg/L for 445 h of continuous operation (influent COD was 178 mg/L), which complied with the China National emission standards of pollutants for the petrochemical industry. Irreversible fouling of the composite membrane, especially caused by monocyclic and oligocyclic aromatic compounds, was alleviated by more than 70 % compared to the pristine PVDF membrane. In addition, it was demonstrated that the cleaning method and type of chemical play a critical role in alleviating irreversible membrane fouling and minimizing the detrimental impact of chemical cleaning on the stability of the modification layer and membrane structure. The results showed that the modified membrane, with its enhanced fouling resistance, high permeability and separation performance, is well-suited as an effective treatment of petrochemical wastewater, offering great potential for widespread use in the application of industrial wastewater treatment and recycling.