The rapid expansion of the chemical and pharmaceutical industries has resulted in the introduction of various sources of micropollutants into the environment, posing threats to drinking water quality and public health. Membrane separation technology offers a promising solution with low energy use, high-quality effluent, and operational simplicity. Here, we developed fluffy layered double hydroxides (LDH)/graphene oxide (GO) 2D membranes, specifically tannic acid-mediated LDH-GO/GO-TA composite membranes (LG/GT). The integration of GO nanosheets regulated the growth of LDH, enhancing electron transfer and adsorption-driven catalytic performance. This design enabled LDH-GO to activate peroxymonosulfate (PMS) and completely degraded Rhodamine B (RhB) within 10 min. The Gaussian calculation was combined with this finding, which could explain the catalytic self-cleaning in the separation process. The TA-mediated enhancement further increased the RhB rejection of LG/GT-7.5 to 99.23%. Additionally, the needle/sheet structure significantly improved permeance to 358.28 L m⁻² h⁻¹ bar⁻¹, surpassing the L/GT-7.5 performance (e.g. 338.53 L m⁻² h⁻¹ bar⁻¹), indicating superior pore formation and water mass transfer. The heterostructure between GO and LDH greatly improved cycling stability, with the membrane maintaining a permeance of 282.71 L m⁻² h⁻¹ bar⁻¹ and a rejection of 97.97% despite 20 cycles. This work demonstrated the potential of fluffy layered LDH 2D membranes for enhanced wastewater treatment applications. These findings suggested significant potential for practical implementation in industrial wastewater treatment processes, offering a sustainable and efficient solution to water pollution challenges.