Recently, oily wastewater is causing serious environmental pollution, and an effective disposal method is highly urgent. Membranes with superhydrophilic and underwater-superoleophobic (SUS) properties have shown prospective advantages. The development of a new nacre-like Li-Bentonite/graphene oxide-calcium carbonate coating membranes (Li-Bent/GO-CaCO3@PVDF CMs) was motivated by the unique mastoid structure of the lotus leaf and the robust layer of the nacre. This CMs were synthesized using a facile, cost-effective, and eco-friendly layer-by-layer (LBL) self-assembly approach. The commercially available polyvinylidene fluoride (PVDF) was utilized as a stable base for the fabrication of the CMs. Among these, GO nanosheets were introduced to imitate the “brick and mortar” structure of mother-of-pearl, and “hard bricks” with interspersed Li-Bent and GO were obtained by the LBL self-assembly method. The phenomenon of “biomineralization” confers an intricate surface structure to the membrane, thereby imparting it with a hydrophilic property of 8.3° and an exceptional non-adhesive behavior in submerged conditions. In addition, the membrane has SUS performance and superior permeability (WF ∼ 5476.3 ± 76 L·m−2·h−1), separation (OF∼3123.78 ± 56 L·m−2·h−1, OR ∼ 99.3 %) and anti-fouling properties (FRR decreased only 14.9 %). Significantly, the membrane has good stability, such as alkali, salt-resistance and aging-resistance. Moreover, this method is easy to operate, and is suitable for surface modification of diversified substrate membranes, with high research and application value.